Aluminosilicate glass with phosphorus and potassium

ABSTRACT

Embodiments of the present invention pertain to antimicrobial glass compositions, glasses and articles. The articles include a glass, which may include a glass phase and a cuprite phase. In other embodiments, the glasses include as plurality of Cu 1+  ions, a degradable phase including B2O3, P 2 O 5  and K 2 O and a durable phase including SiO 2 . Other embodiments include glasses having a plurality of Cu 1+  ions disposed on the surface of the glass and in the glass network and/or the glass matrix. The article may also include a polymer. The glasses and articles disclosed herein exhibit a 2 log reduction or greater in a concentration of at least one of  Staphylococcus aureus, Enterobacter aerogenes, Pseudomomas aeruginosa  bacteria, Methicillin Resistant  Staphylococcus aureus , and  E. coli , under the EPA Test Method for Efficacy of Copper Alloy as a Sanitizer testing condition and under Modified JIS Z 2801 for Bacteria testing conditions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application is a continuation of U.S. application Ser. No.17/321,905 filed May 17, 2021, which is a continuation of U.S.application Ser. No. 16/037,762 filed Jul. 17, 2018, which issued onJun. 22, 2021 as U.S. Pat. No. 11,039,620 and is a continuation-in-partof U.S. application Ser. No. 15/446,223 filed Mar. 1, 2017, which issuedon Jun. 22, 2021 as U.S. Pat. No. 11,039,619 and is a division of U.S.application Ser. No. 14/623,077 filed Feb. 16, 2015, which issued onApril 18, 2017 as U.S. Pat. No. 9,622,483 and claims priority to U.S.Application Nos. 62/034,842 filed Aug. 8, 2014, 62/034,834 filed Aug. 8,2014, 62/026,186 filed Jul. 18, 2014, 62/026,177 filed Jul. 18, 2014,61/992,987 filed May 14, 2014, 61/992,980 filed May 14, 2014, 61/941,690filed Feb. 19, 2014, and 61/941,677 filed Feb. 19, 2014, each of whichabove applications is hereby incorporated by reference herein in itsentirety.

BACKGROUND

The present disclosure relates generally to antimicrobial glasscompositions and articles incorporating such compositions. Moreparticularly, the various embodiments described herein relate to glasseshaving antimicrobial attributes and articles that incorporate suchglasses.

Consumer electronics articles, including touch-activated ortouch-interactive devices, such as screen surfaces (e.g., surfaces ofelectronic devices having user-interactive capabilities that areactivated by touching specific portions of the surfaces), have becomeincreasingly more prevalent. As the extent to which the touchscreen-based interactions between a user and a device increases, so toodoes the likelihood of the surface harboring microorganisms (e.g.,bacteria, fungi, viruses, and the like) that can be transferred fromuser to user. Moreover, the housings which incorporate thetouch-activated or touch-interactive devices also include surfaces thatharbor such microorganisms that can be transferred from user to user.The concern of microorganism transfer is also a concern with equipment,furniture and architectural articles used in medical or office settingsand many other articles in which users come into contact with surfaces.

To minimize the presence of microbes on various materials, so-called“antimicrobial” properties have been imparted to a variety of glasses;however, there is a need to provide entire articles (including thehousing and any glasses used as cover glass) that also exhibitantimicrobial properties. Accordingly, antimicrobial articles useful forcertain applications should be durable enough for the purpose for whichthey are used, while also providing continuous antimicrobial propertiesthat are passive or do not require additional activation by a user oroutside source (e.g., UV light). In addition, antimicrobial glasses andarticles should provide controlled antimicrobial activity.

SUMMARY

A first aspect of the present disclosure pertains to an article thatincludes a carrier and a glass. Examples of suitable carriers includepolymers, monomers, binders, solvents, and other materials used to formmolded articles, formed articles, coatings on substrates or other sucharticles. Exemplary coatings may include anti-frictive coatings,coatings exhibiting a low coefficient of friction, or coatings that forma surface exhibiting a low coefficient of friction.

The glass of one or more embodiments may also include a composition thatincludes, in mole percent: SiO₂ in the range from about 40 to about 70,Al₂O₃ in the range from about 0 to about 20, a copper-containing oxidein the range from about 10 to about 50, CaO in the range from about 0 toabout 15, MgO in the range from about 0 to about 15, P₂O₅ in the rangefrom about 0 to about 25, B₂O₃ in the range from about 0 to about 25,K₂O in the range from about 0 to about 20, ZnO in the range from about 0to about 5, Na₂O in the range from about 0 to about 20, and Fe₂O₃ in therange from about 0 to about 5. In some embodiments, the amount ofcopper-containing oxide is greater than the amount of Al₂O₃ (which maybe about 5 mole percent or less, in some cases). In some instances, thecomposition may be free of Al₂O₃. Examples of suitable copper-containingoxides can include CuO, Cu₂O, or a combination thereof.

The article of one or more embodiments may include a plurality of Cu¹⁺ions, Cu metal or a combination thereof. In some instances, the glassmay be substantially free of tenorite.

The glass of one or more embodiments may include a cuprite phase and aglass phase. In some embodiments, the cuprite phase may include crystalsthat have an average major dimension of about 5 micrometers (μm) orless, or even about 1 micrometer (μm) or less.

A second aspect of the present disclosure pertains to an article thatincludes a carrier and a glass with a plurality of Cu¹⁺ ions, adegradable phase comprising at least one of B₂O₃, P₂O₅ and R₂O, and adurable phase comprising SiO₂. The glass may be formed from thecompositions described herein. In some instances, the durable phase ispresent in an amount by weight that is greater than the degradablephase. The degradable phase of one or more embodiments leaches or isleachable in the presence of water.

The article may optionally include a cuprite phase, which may bedispersed in one or both of the degradable phase and the durable phase.The cuprite phase may have crystals having an average major dimension ofabout 5 micrometers (μm) or less, about 1 micrometer (μm) or less, orabout 500 nanometers (nm) or less. The cuprite phase may comprise atleast about 10 weight percent or at least about 20 weight percent of theglass.

In one or more embodiments, the glass includes a surface portion (havinga depth of less than about 5 nanometers (nm)) that includes a pluralityof copper ions. In some embodiments, at least 75% of the plurality ofcopper ions is Cu¹⁺. In other embodiments, less than about 25% of theplurality of copper ions is Cu²⁺.

A third aspect of the present disclosure pertains to an articleincluding a carrier; and an inorganic material, wherein the inorganicmaterial comprises a surface and a plurality of Cu¹⁺ ions disposed onthe surface. The inorganic material may include a glass and may beformed form the compositions described herein. The inorganic materialmay be substantially free of tenorite.

In one or more embodiments, the plurality of Cu¹⁺ ions may be dispersedin a glass network and/or a glass matrix. In some instances, the glassnetwork includes atoms to which the plurality of Cu¹⁺ ions is atomicallybonded. The plurality of Cu¹⁺ ions may include cuprite crystals that aredispersed in the glass matrix.

The carrier may include a polymer, a monomer, a binder, a solvent, orcombinations thereof. Carriers may include anti-frictive materials suchas for example, fluorocarbons, fluorinated silanes, and alkylperfluorocarbon silanes. The polymer used in the embodiments describedherein can include organic or inorganic polymers. Exemplary polymers mayinclude a thermoplastic polymer, a polyolefin, a cured polymer, anultraviolet- or UV-cured polymer, a polymer emulsion, a solvent-basedpolymer, and combinations thereof. Specific examples of monomers includecatalyst curable monomers, thermally-curable monomers, radiation-curablemonomers and combinations thereof. The articles described herein mayinclude a glass to carrier ratio in the range from about 10:90 to about90:10, based on weight percent.

The glasses and articles described herein may exhibit a 2 log reductionor greater in a concentration of at least one of Staphylococcus aureus,Enterobacter aerogenes, Pseudomomas aeruginosa bacteria, MethicillinResistant Staphylococcus aureus, and E. coli, under the EPA Test Methodfor Efficacy of Copper Alloy as a Sanitizer testing conditions(hereinafter, the “EPA Test”).

The glasses and articles described herein according to one or moreembodiments may exhibit a 4 log reduction or greater (e.g., 5 logreduction or greater) in a concentration of at least one ofStaphylococcus aureus, Enterobacter aerogenes, Pseudomomas aeruginosabacteria, Methicillin Resistant Staphylococcus aureus, and E. coli,under JIS Z 2801 (2000) testing conditions. One or more embodiments ofthe glasses and articles described herein also exhibit a 4 log reductionor greater (e.g., 5 log reduction or greater) in a concentration of atleast one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomomasaeruginosa, Methicillin Resistant Staphylococcus aureus, and E. coli,under modified JIS Z 2801 (2000) testing conditions (hereinafter,“Modified JIS Z 2801 Test for Bacteria”). The Modified JIS Z 2801 (2000)Test for Bacteria is described in greater detail herein.

In one or more embodiments, the glasses and articles described hereinaccording to one or more embodiments may exhibit a 2 log reduction orgreater (e.g., 4 log reduction or greater, or a 5 log reduction orgreater) in a concentration of Murine Norovirus, under modified JIS Z2801 (2000) testing conditions for evaluating viruses (hereinafter,“Modified JIS Z 2801 for Viruses”). The Modified JIS Z 2801 (2000) Testfor Viruses is described in greater detail herein.

In some embodiments, the glasses and articles may exhibit the logreductions described herein (i.e., under the EPA Test, the JIS Z 2801testing conditions, the Modified JIS Z 2801 Test for Bacteria and/or theModified JIS Z 2801 Test for Viruses), for a period of one month orgreater or for a period of three months or greater. The one month periodor three month period may commence at or after the formation of theglass, or at or after combination of the glass with a carrier.

In one or more embodiments, the articles leach the copper ions whenexposed or in contact with a leachate. In one or more embodiments, thearticles leach only copper ions when exposed to leachates includingwater.

The articles described herein may form the housing for an electronicdevice.

A fourth aspect of the present disclosure pertains to a method of makingan antimicrobial article. In one or more embodiments, the methodincludes melting a glass composition to form a glass comprising aplurality of Cu¹⁺ ions; and a glass phase, forming the glass into atleast one of particulates and fibers, dispersing the at least one ofparticulates and fibers in a carrier, such as a polymer (as describedherein), a monomer, or a binder, to provide a filled carrier and formingthe filled carrier into the antimicrobial article. The glass compositionmay include the compositions described herein.

Additional features and advantages will be set forth in the detaileddescription which follows, and in part will be readily apparent to thoseskilled in the art from that description or recognized by practicing theembodiments as described herein, including the detailed descriptionwhich follows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description andthe following detailed description are merely exemplary, and areintended to provide an overview or framework to understanding the natureand character of the claims. The accompanying drawings are included toprovide a further understanding, and are incorporated in and constitutea part of this specification. The drawings illustrate one or moreembodiment(s), and together with the description serve to explainprinciples and operation of the various embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a side view of an antimicrobial glass in the form of a sheetaccording to one or more embodiments;

FIG. 2 is an enlarged partial view of the antimicrobial glass shown inFIG. 1.

FIG. 3 is a transmission electron microscopy (TEM) image of anantimicrobial glass, according to one or more embodiments;

FIG. 4 is a scanning electron microscopy (SEM) image of a cross-sectionof the antimicrobial glass shown in FIG. 3;

FIG. 5 is a SEM image of a fracture cross-section of the antimicrobialglass shown in FIG. 3;

FIG. 6 is an SEM image of the antimicrobial glass according to one ormore embodiments;

FIG. 7A is a SEM-energy-dispersive X-ray spectroscopy (EDX) hypermap ofa cross-section of Example 30, after being annealed overnight at 650° C.after melting at 1650° C.;

FIG. 7B is a SEM-EDX hypermap of a cross-section of Example 30 afterbeing quenched in water after melting at 1650° C.;

FIG. 8A shows a fracture cross-section of Example 30, after anadditional heat treatment at 800° C. for 1 hour;

FIG. 8B shows a polished cross-section of Example 30, after anadditional heat treatment at 800° C. for 1 hour;

FIG. 9 illustrates the antimicrobial activity of glasses according toone or more embodiments;

FIG. 10 is a graph showing the antimicrobial activity of anantimicrobial glass described herein, when formed into particles andcombined with a polymer carrier, after various time periods;

FIG. 11 is a graph illustrating the antimicrobial activity of variousarticles, according one or more embodiments;

FIG. 12 is a graph illustrating the antimicrobial activity of variousarticles, according to one or more embodiments;

FIG. 13 is a graph illustrating the antimicrobial activity of glasseshaving different amounts of copper;

FIG. 14 shows images of injection molded articles made from Example 12and a polymer; and

FIG. 15 shows the antimicrobial activity of injection molded articles,according to one or more embodiments, with and without different surfacetreatments.

DETAILED DESCRIPTION

Reference will now be made in detail to various embodiment(s), examplesof which are illustrated in the accompanying drawings.

A first aspect of the present disclosure pertains to antimicrobial glasscompositions and glasses made from or including such compositions. Theantimicrobial properties of the glasses disclosed herein includeantiviral and/or antibacterial properties. As used herein the term“antimicrobial,” means a material, or a surface of a material that willkill or inhibit the growth of bacteria, viruses and/or fungi. The termas used herein does not mean the material or the surface of the materialwill kill or inhibit the growth of all species microbes within suchfamilies, but that it will kill or inhibit the growth of one or morespecies of microbes from such families.

As used herein the term “log reduction” means−log (C_(a)/C₀), whereC_(a)=the colony form unit (CFU) number of the antimicrobial surface andC₀=the colony form unit (CFU) of the control surface that is not anantimicrobial surface. As an example, a 3 log reduction equals about99.9% of the bacteria, viruses and/or fungi killed and a Log Reductionof 5=99.999% of bacteria, viruses and/or fungi killed.

In one or more embodiments, the antimicrobial glasses include a Cuspecies. In one or more alternative embodiments, the Cu species mayinclude Cu¹⁺, Cu⁰, and/or Cu²⁺. The combined total of the Cu species maybe about 10 wt % or more. However, as will be discussed in more detailbelow, the amount of Cu²⁺ is minimized or is reduced such that theantimicrobial glass is substantially free of Cu²⁺. The Cu¹⁺ ions may bepresent on or in the surface and/or the bulk of the antimicrobial glass.In some embodiments, the Cu¹⁺ ions are present in the glass networkand/or the glass matrix of the antimicrobial glass. Where the Cu¹⁺ ionsare present in the glass network, the Cu¹⁺ ions are atomically bonded tothe atoms in the glass network. Where the Cu¹⁺ ions are present in theglass matrix, the Cu¹⁺ ions may be present in the form of Cu¹⁺ crystalsthat are dispersed in the glass matrix. In some embodiments the Cu¹⁺crystals include cuprite (Cu₂O). In such embodiments, where Cu¹⁺crystals are present, the material may be referred to as anantimicrobial glass ceramic, which is intended to refer to a specifictype of glass with crystals that may or may not be subjected to atraditional ceramming process by which one or more crystalline phasesare introduced and/or generated in the glass. Where the Cu¹⁺ ions arepresent in a non-crystalline form, the material may be referred to as anantimicrobial glass. In some embodiments, both Cu Cu¹⁺ crystals and Cu¹⁺ions not associated with a crystal are present in the antimicrobialglasses described herein.

In one or more embodiments, the antimicrobial glass may be formed from acomposition that can include, in mole percent, SiO₂ in the range fromabout 40 to about 70, Al₂O₃ in the range from about 0 to about 20, acopper-containing oxide in the range from about 10 to about 30, CaO inthe range from about 0 to about 15, MgO in the range from about 0 toabout 15, P₂O₅ in the range from about 0 to about 25, B₂O₃ in the rangefrom about 0 to about 25, K₂O in the range from about 0 to about 20, ZnOin the range from about 0 to about 5, Na₂O in the range from about 0 toabout 20, and/or Fe₂O₃ in the range from about 0 to about 5. In suchembodiments, the amount of the copper-containing oxide is greater thanthe amount of Al₂O₃. In some embodiments, the composition may include acontent of R₂O, where R may include K, Na, Li, Rb, Cs and combinationsthereof.

In the embodiments of the compositions described herein, SiO₂ serves asthe primary glass-forming oxide. The amount of SiO₂ present in acomposition should be enough to provide glasses that exhibit therequisite chemical durability suitable for its use or application (e.g.,touch applications, article housing etc.). The upper limit of SiO₂ maybe selected to control the melting temperature of the compositionsdescribed herein. For example, excess SiO₂ could drive the meltingtemperature at 200 poise to high temperatures at which defects such asfining bubbles may appear or be generated during processing and in theresulting glass. Furthermore, compared to most oxides, SiO₂ decreasesthe compressive stress created by an ion exchange process of theresulting glass. In other words, glass formed from compositions withexcess SiO₂ may not be ion-exchangeable to the same degree as glassformed from compositions without excess SiO₂. Additionally oralternatively, SiO₂ present in the compositions according to one or moreembodiments could increase the plastic deformation prior breakproperties of the resulting glass. An increased SiO₂ content in theglass formed from the compositions described herein may also increasethe indentation fracture threshold of the glass.

In one or more embodiments, the composition includes SiO₂ in an amount,in mole percent, in the range from about 40 to about 70, from about 40to about 69, from about 40 to about 68, from about 40 to about 67, fromabout 40 to about 66, from about 40 to about 65, from about 40 to about64, from about 40 to about 63, from about 40 to about 62, from about 40to about 61, from about 40 to about 60, from about 41 to about 70, fromabout 42 to about 70, from about 43 to about 70, from about 44 to about70, from about 45 to about 70, from about 46 to about 70, from about 47to about 70, from about 48 to about 70, from about 49 to about 70, fromabout 50 to about 70, from about 41 to about 69, from about 42 to about68, from about 43 to about 67, from about 44 to about 66, from about 45to about 65, from about 46 to about 64, from about 47 to about 63, fromabout 48 to about 62, from about 49 to about 61, from about 50 to about60 and all ranges and sub-ranges therebetween.

In one or more embodiments, the composition includes Al₂O₃ an amount, inmole percent, in the range from about 0 to about 20, from about 0 toabout 19, from about 0 to about 18, from about 0 to about 17, from about0 to about 16, from about 0 to about 15, from about 0 to about 14, fromabout 0 to about 13, from about 0 to about 12, from about 0 to about 11from about 0 to about 10, from about 0 to about 9, from about 0 to about8, from about 0 to about 7, from about 0 to about 6, from about 0 toabout 5, from about 0 to about 4, from about 0 to about 3, from about 0to about 2, from about 0 to about 1, from about 0.1 to about 1, fromabout 0.2 to about 1, from about 0.3 to about 1, from about 0.4 to about1, from about 0.5 to about 1, from about 0 to about 0.5, from about 0 toabout 0.4, from about 0 to about 0.3, from about 0 to about 0.2, fromabout 0 to about 0.1 and all ranges and sub-ranges therebetween. In someembodiments, the composition is substantially free of Al₂O₃. As usedherein, the phrase “substantially free” with respect to the componentsof the composition and/or resulting glass means that the component isnot actively or intentionally added to the compositions during initialbatching or subsequent post processing (e.g., ion exchange process), butmay be present as an impurity. For example, a composition, a glass maybe described as being substantially free of a component, when thecomponent is present in an amount of less than about 0.01 mol %.

The amount of Al₂O₃ may be adjusted to serve as a glass-forming oxideand/or to control the viscosity of molten compositions. Without beingbound by theory, it is believed that when the concentration of alkalioxide (R₂O) in a composition is equal to or greater than theconcentration of Al₂O₃, the aluminum ions are found in tetrahedralcoordination with the alkali ions acting as charge-balancers. Thistetrahedral coordination greatly enhances various post-processing (e.g.,ion exchange process) of glasses formed from such compositions. Divalentcation oxides (RO) can also charge balance tetrahedral aluminum tovarious extents. While elements such as calcium, zinc, strontium, andbarium behave equivalently to two alkali ions, the high field strengthof magnesium ions causes them to not fully charge balance aluminum intetrahedral coordination, resulting in the formation of five- andsix-fold coordinated aluminum. Generally, A1₂0₃ can play an importantrole in ion-exchangeable compositions and strengthened glasses since itenables a strong network backbone (i.e., high strain point) whileallowing for the relatively fast diffusivity of alkali ions. However,when the concentration of Al₂O₃ is too high, the composition may exhibitlower liquidus viscosity and, thus, Al₂O₃ concentration may becontrolled within a reasonable range. Moreover, as will be discussed inmore detail below, excess Al₂O₃ has been found to promote the formationof Cu¹⁺ ions, instead of the desired Cu¹⁺ ions.

In one or more embodiments, the composition includes a copper-containingoxide in an amount, in mole percent, in the range from about 10 to about50, from about 10 to about 49, from about 10 to about 48, from about 10to about 47, from about 10 to about 46, from about 10 to about 45, fromabout 10 to about 44, from about 10 to about 43, from about 10 to about42, from about 10 to about 41, from about 10 to about 40, from about 10to about 39, from about 10 to about 38, from about 10 to about 37, fromabout 10 to about 36, from about 10 to about 35, from about 10 to about34, from about 10 to about 33, from about 10 to about 32, from about 10to about 31, from about 10 to about 30, from about 10 to about 29, fromabout 10 to about 28, from about 10 to about 27, from about 10 to about26, from about 10 to about 25, from about 10 to about 24, from about 10to about 23, from about 10 to about 22, from about 10 to about 21, fromabout 10 to about 20, from about 11 to about 50, from about 12 to about50, from about 13 to about 50, from about 14 to about 50, from about 15to about 50, from about 16 to about 50, from about 17 to about 50, fromabout 18 to about 50, from about 19 to about 50, from about 20 to about50, from about 10 to about 30, from about 11 to about 29, from about 12to about 28, from about 13 to about 27, from about 14 to about 26, fromabout 15 to about 25, from about 16 to about 24, from about 17 to about23, from about 18 to about 22, from about 19 to about 21 and all rangesand sub-ranges therebetween. In one or more specific embodiments, thecopper-containing oxide may be present in the composition in an amountof about 20 mole percent, about 25 mole percent, about 30 mole percentor about 35 mole percent. The copper-containing oxide may include CuO,Cu₂O and/or combinations thereof.

The copper-containing oxides in the composition form the Cu¹⁺ ionspresent in the resulting glass. Copper may be present in the compositionand/or the glasses including the composition in various forms includingCu° , Cu¹⁺, and Cu²⁺. Copper in the Cu⁰ or Cu¹⁺ forms provideantimicrobial activity. However forming and maintaining these states ofantimicrobial copper are difficult and often, in known compositions,Cu²⁺ ions are formed instead of the desired Cu⁰ or Cu¹⁺ ions.

In one or more embodiments, the amount of copper-containing oxide isgreater than the amount of Al₂O₃ in the composition. Without being boundby theory it is believed that an about equal amount of copper-containingoxides and Al₂O₃ in the composition results in the formation of tenorite(CuO) instead of cuprite (Cu₂O). The presence of tenorite decreases theamount of Cu¹⁺ in favor of Cu²⁺ and thus leads to reduced antimicrobialactivity. Moreover, when the amount of copper-containing oxides is aboutequal to the amount of Al₂O₃, aluminum prefers to be in a four-foldcoordination and the copper in the composition and resulting glassremains in the Cu²⁺ form so that the charge remains balanced. Where theamount of copper-containing oxide exceeds the amount of Al₂O₃, then itis believed that at least a portion of the copper is free to remain inthe Cu¹⁺ state, instead of the Cu²⁺ state, and thus the presence of Cu¹⁺ions increases.

The composition of one or more embodiments includes P₂O₅ in an amount,in mole percent, in the range from about 0 to about 25, from about 0 toabout 22, from about 0 to about 20, from about 0 to about 18, from about0 to about 16, from about 0 to about 15, from about 0 to about 14, fromabout 0 to about 13, from about 0 to about 12, from about 0 to about 11,from about 0 to about 10, from about 0 to about 9, from about 0 to about8, from about 0 to about 7, from about 0 to about 6, from about 0 toabout 5, from about 0 to about 4, from about 0 to about 3, from about 0to about 2, from about 0 to about 1, from about 0.1 to about 1, fromabout 0.2 to about 1, from about 0.3 to about 1, from about 0.4 to about1, from about 0.5 to about 1, from about 0 to about 0.5, from about 0 toabout 0.4, from about 0 to about 0.3 from about 0 to about 0.2, fromabout 0 to about 0.1 and all ranges and sub-ranges therebetween. In someembodiments, the composition includes about 10 mole percent or about 5mole percent P₂O₅ or, alternatively, may be substantially free of P₂O₅.

In one or more embodiments, P₂O₅ forms at least part of a less durablephase or a degradable phase in the glass. The relationship between thedegradable phase(s) of the glass and antimicrobial activity is discussedin greater detail herein. In one or more embodiments, the amount of P₂O₅may be adjusted to control crystallization of the composition and/orglass during forming. For example, when the amount of P₂O₅ is limited toabout 5 mol % or less or even 10 mol % or less, crystallization may beminimized or controlled to be uniform. However, in some embodiments, theamount or uniformity of crystallization of the composition and/or glassmay not be of concern and thus, the amount of P2O5 utilized in thecomposition may be greater than 10 mol %.

In one or more embodiments, the amount of P2O5 in the composition may beadjusted based on the desired damage resistance of the glass, despitethe tendency for P₂O₅ to form a less durable phase or a degradable phasein the glass. Without being bound by theory, P₂O₅ can decrease themelting viscosity relative to SiO₂. In some instances, P₂O₅ is believedto help to suppress zircon breakdown viscosity (i.e., the viscosity atwhich zircon breaks down to form ZrO₂) and may be more effective in thisregard than SiO₂. When glass is to be chemically strengthened via an ionexchange process, P₂O₅ can improve the diffusivity and decrease ionexchange times, when compared to other components that are sometimescharacterized as network formers (e.g., SiO₂ and/or B₂O₃).

The composition of one or more embodiments includes B₂O₃ in an amount,in mole percent, in the range from about 0 to about 25, from about 0 toabout 22, from about 0 to about 20, from about 0 to about 18, from about0 to about 16, from about 0 to about 15, from about 0 to about 14, fromabout 0 to about 13, from about 0 to about 12, from about 0 to about 11,from about 0 to about 10, from about 0 to about 9, from about 0 to about8, from about 0 to about 7, from about 0 to about 6, from about 0 toabout 5, from about 0 to about 4, from about 0 to about 3, from about 0to about 2, from about 0 to about 1, from about 0.1 to about 1, fromabout 0.2 to about 1, from about 0.3 to about 1, from about 0.4 to about1, from about 0.5 to about 1, from about 0 to about 0.5, from about 0 toabout 0.4, from about 0 to about 0.3, from about 0 to about 0.2, fromabout 0 to about 0.1 and all ranges and sub-ranges therebetween. In someembodiments, the composition includes a non-zero amount of B₂O₃, whichmay be, for example, about 10 mole percent or about 5 mole percent. Thecomposition of some embodiments may be substantially free of B₂O₃.

In one or more embodiments, B₂O₃ forms a less durable phase or adegradable phase in the glass formed form the composition. Therelationship between the degradable phase(s) of the glass andantimicrobial activity is discussed in greater detail herein. Withoutbeing bound by theory, it is believed the inclusion of B₂O₃ incompositions imparts damage resistance in glasses incorporating suchcompositions, despite the tendency for B₂O₃ to form a less durable phaseor a degradable phase in the glass. The composition of one or moreembodiments includes one or more alkali oxides (R₂O) (e.g., Li₂O, Na₂O,K₂O, Rb₂O and/or Cs₂O). In some embodiments, the alkali oxides modifythe melting temperature and/or liquidus temperatures of suchcompositions. In one or more embodiments, the amount of alkali oxidesmay be adjusted to provide a composition exhibiting a low meltingtemperature and/or a low liquidus temperature. Without being bound bytheory, the addition of alkali oxide(s) may increase the coefficient ofthermal expansion (CTE) and/or lower the chemical durability of theantimicrobial glasses that include such compositions. In some casesthese attributes may be altered dramatically by the addition of alkalioxide(s).

In some embodiments, the antimicrobial glasses disclosed herein may bechemically strengthened via an ion exchange process in which thepresence of a small amount of alkali oxide (such as Li₂O and Na₂O) isrequired to facilitate ion exchange with larger alkali ions (e.g., K⁺),for example exchanging smaller alkali ions from an antimicrobial glasswith larger alkali ions from a molten salt bath containing such largeralkali ions. Three types of ion exchange can generally be carried out.One such ion exchange includes a Na⁺-for-Li⁺ exchange, which results ina deep depth of layer but low compressive stress. Another such ionexchange includes a K⁺-for-Li⁺ exchange, which results in a small depthof layer but a relatively large compressive stress. A third such ionexchange includes a K⁺-for-Na⁺ exchange, which results in intermediatedepth of layer and compressive stress. A sufficiently high concentrationof the small alkali oxide in compositions may be necessary to produce alarge compressive stress in the antimicrobial glass including suchcompositions, since compressive stress is proportional to the number ofalkali ions that are exchanged out of the antimicrobial glass.

In one or more embodiments, the composition includes K₂O in an amount inthe range from about 0 to about 20, from about 0 to about 18, from about0 to about 16, from about 0 to about 15, from about 0 to about 14, fromabout 0 to about 13, from about 0 to about 12, from about 0 to about 11,from about 0 to about 10, from about 0 to about 9, from about 0 to about8, from about 0 to about 7, from about 0 to about 6, from about 0 toabout 5, from about 0 to about 4, from about 0 to about 3, from about 0to about 2, from about 0 to about 1, from about 0.1 to about 1, fromabout 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 toabout 0.4, from about 0 to about 0.3 from about 0 to about 0.2, fromabout 0 to about 0.1 and all ranges and sub-ranges therebetween. In someembodiments, the composition includes a non-zero amount of K₂O or,alternatively, the composition may be substantially free, as definedherein, of K₂O. In addition to facilitating ion exchange, whereapplicable, in one or more embodiments, K₂O can also form a less durablephase or a degradable phase in the glass formed form the composition.The relationship between the degradable phase(s) of the glass andantimicrobial activity is discussed in greater detail herein.

In one or more embodiments, the composition includes Na₂O in an amountin the range from about 0 to about 20, from about 0 to about 18, fromabout 0 to about 16, from about 0 to about 15, from about 0 to about 14,from about 0 to about 13, from about 0 to about 12, from about 0 toabout 11, from about 0 to about 10, from about 0 to about 9, from about0 to about 8, from about 0 to about 7, from about 0 to about 6, fromabout 0 to about 5, from about 0 to about 4, from about 0 to about 3,from about 0 to about 2, from about 0 to about 1, from about 0.1 toabout 1, from about 0.2 to about 1, from about 0.3 to about 1, fromabout 0.4 to about 1, from about 0.5 to about 1, from about 0 to about0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0to about 0.2, from about 0 to about 0.1 and all ranges and sub-rangestherebetween. In some embodiments, the composition includes a non-zeroamount of Na₂O or, alternatively, the composition may be substantiallyfree, as defined herein, of Na₂O.

In one or more embodiments, the composition may include one or moredivalent cation oxides, such as alkaline earth oxides and/or ZnO. Suchdivalent cation oxides may be included to improve the melting behaviorof the compositions. With respect to ion exchange performance, thepresence of divalent cations can act to decrease alkali mobility andthus, when larger divalent cation oxides are utilized, there may be anegative effect on ion exchange performance. Furthermore, smallerdivalent cation oxides generally help the compressive stress developedin an ion-exchanged glass more than the larger divalent cation oxides.Hence, divalent cation oxides such as MgO and ZnO can offer advantageswith respect to improved stress relaxation, while minimizing the adverseeffects on alkali diffusivity.

In one or more embodiments, the composition includes CaO in an amount,in mole percent, in the range from about 0 to about 15, from about 0 toabout 14, from about 0 to about 13, from about 0 to about 12, from about0 to about 11, from about 0 to about 10, from about 0 to about 9, fromabout 0 to about 8, from about 0 to about 7, from about 0 to about 6,from about 0 to about 5, from about 0 to about 4, from about 0 to about3, from about 0 to about 2, from about 0 to about 1, from about 0.1 toabout 1, from about 0.2 to about 1, from about 0.3 to about 1, fromabout 0.4 to about 1, from about 0.5 to about 1, from about 0 to about0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0to about 0.2, from about 0 to about 0.1 and all ranges and sub-rangestherebetween. In some embodiments, the composition is substantially freeof CaO.

In one or more embodiments, the composition includes MgO in an amount, mmole percent, in the range from about 0 to about 15, from about 0 toabout 14, from about 0 to about 13, from about 0 to about 12, from about0 to about 11, from about 0 to about 10, from about 0 to about 9, fromabout 0 to about 8, from about 0 to about 7, from about 0 to about 6,from about 0 to about 5, from about 0 to about 4, from about 0 to about3, from about 0 to about 2, from about 0 to about 1, from about 0.1 toabout 1, from about 0.2 to about 1, from about 0.3 to about 1, fromabout 0.4 to about 1, from about 0.5 to about 1, from about 0 to about0.5, from about 0 to about 0.4, from about 0 to about 0.3, from about 0to about 0.2, from about 0 to about 0.1 and all ranges and sub-rangestherebetween. In some embodiments, the composition is substantially freeof MgO.

The composition of one or more embodiments may include ZnO in an amount,in mole percent, in the range from about 0 to about 5, from about 0 toabout 4, from about 0 to about 3, from about 0 to about 2, from about 0to about 1, from about 0.1 to about 1, from about 0.2 to about 1, fromabout 0.3 to about 1, from about 0.4 to about 1, from about 0.5 to about1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 toabout 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and allranges and sub-ranges therebetween. In some embodiments, the compositionis substantially free of ZnO.

The composition of one or more embodiments may include Fe₂O₃, in molepercent, in the range from about 0 to about 5, from about 0 to about 4,from about 0 to about 3, from about 0 to about 2, from about 0 to about1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3to about 1, from about 0.4 to about 1, from about 0.5 to about 1, fromabout 0 to about 0.5, from about 0 to about 0.4, from about 0 to about0.3, from about 0 to about 0.2, from about 0 to about 0.1 and all rangesand sub-ranges therebetween. In some embodiments, the composition issubstantially free of Fe₂O₃.

In one or more embodiments, the composition may include one or morecolorants. Examples of such colorants include NiO, TiO₂, Fe₂O₃, Cr₂O₃,Co₃O₄ and other known colorants. In some embodiments, the one or morecolorants may be present in an amount in the range up to about 10 mol %.In some instances, the one or more colorants may be present in an amountin the range from about 0.01 mol % to about 10 mol %, from about 1 mol %to about 10 mol %, from about 2 mol % to about 10 mol %, from about 5mol % to about 10 mol %, from about 0.01 mol % to about 8 mol %, or fromabout 0.01 mol % to about 5 mol %.

In one or more embodiments, the composition may include one or morenucleating agents. Exemplary nucleating agents include TiO₂, ZrO₂ andother known nucleating agents in the art. The composition can includeone or more different nucleating agents. The nucleating agent content ofthe composition may be in the range from about 0.01 mol % to about 1 mol%. In some instances, the nucleating agent content may be in the rangefrom about 0.01 mol % to about 0.9 mol %, from about 0.01 mol % to about0.8 mol %, from about 0.01 mol % to about 0.7 mol %, from about 0.01 mol% to about 0.6 mol %, from about 0.01 mol % to about 0.5 mol %, fromabout 0.05 mol % to about 1 mol %, from about 0.1 mol % to about 1 mol%, from about 0.2 mol % to about 1 mol %, from about 0.3 mol % to about1 mol %, or from about 0.4 mol % to about 1 mol %, and all ranges andsub-ranges therebetween.

The glasses formed from the compositions may include a plurality of Cu¹⁺ions. In some embodiments, such Cu¹⁺ ions form part of the glass networkand may be characterized as a glass modifier. Without being bound bytheory, where Cu¹⁺ ions are part of the glass network, it is believedthat during typical glass formation processes, the cooling step of themolten glass occurs too rapidly to allow crystallization of thecopper-containing oxide (e.g., CuO and/or Cu₂O). Thus the Cu¹⁺ remainsin an amorphous state and becomes part of the glass network. In somecases, the total amount of Cu¹⁺ ions, whether they are in a crystallinephase or in the glass matrix, may be even higher, such as up to 40 mol%, up to 50 mol %, or up to 60 mol %.

In one or more embodiments, the glasses formed form the compositionsdisclosed herein include Cu¹⁺ ions that are dispersed in the glassmatrix as Cu¹⁺ crystals. In one or more embodiments, the Cu¹⁺ crystalsmay be present in the form of cuprite. The cuprite present in the glassmay form a phase that is distinct from the glass matrix or glass phase.In other embodiments, the cuprite may form part of or may be associatedwith one or more glasses phases (e.g., the durable phase describedherein). The Cu¹⁺ crystals may have an average major dimension of about5 micrometers (μm) or less, 4 micrometers (μm) or less, 3 micrometers(μm) or less, 2 micrometers (μm) or less, about 1.9 micrometers (μm) orless, about 1.8 micrometers (μm) or less, about 1.7 micrometers (μm) orless, about 1.6 micrometers (μm) or less, about 1.5 micrometers (μm) orless, about 1.4 micrometers (μm) or less, about 1.3 micrometers (μm) orless, about 1.2 micrometers (μm) or less, about 1.1 micrometers or less,1 micrometers or less, about 0.9 micrometers (μm) or less, about 0.8micrometers (μm) or less, about 0.7 micrometers (μm) or less, about 0.6micrometers (μm) or less, about 0.5 micrometers (μm) or less, about 0.4micrometers (μm) or less, about 0.3 micrometers (μm) or less, about 0.2micrometers (μm) or less, about 0.1 micrometers (μm) or less, about 0.05micrometers (μm) or less, and all ranges and sub-ranges therebetween. Asused herein and with respect to the phrase “average major dimension”,the word “average” refers to a mean value and the word “major dimension”is the greatest dimension of the particle as measured by SEM. In someembodiments, the cuprite phase may be present in the antimicrobial glassin an amount of at least about 10 wt %, at least about 15 wt %, at leastabout 20 wt %, at least about 25 wt % and all ranges and subrangestherebetween of the antimicrobial glass.

In some embodiments, the glasses may include about 70 wt % Cu¹⁺ or moreand about 30 wt % of Cu²⁺ or less. The Cu²⁺ ions may be present intenorite form and/or even in the glass (i.e., not as a crystallinephase).

In some embodiments, the total amount of Cu by wt % in the glasses maybe in the range from about 10 to about 30, from about 15 to about 25,from about 11 to about 30, from about 12 to about 30, from about 13 toabout 30, from about 14 to about 30, from about 15 to about 30, fromabout 16 to about 30, from about 17 to about 30, from about 18 to about30, from about 19 to about 30, from about 20 to about 30, from about 10to about 29, from about 10 to about 28, from about 10 to about 27, fromabout 10 to about 26, from about 10 to about 25, from about 10 to about24, from about 10 to about 23, from about 10 to about 22, from about 10to about 21, from about 10 to about 20, from about 16 to about 24, fromabout 17 to about 23, from about 18 to about 22, from about 19 to about21 and all ranges and sub-ranges therebetween. In one or moreembodiments, the ratio of Cu¹⁺ ions to the total amount Cu in the glassis about 0.5 or greater, 0.55 or greater, 0.6 or greater, 0.65 orgreater, 0.7 or greater, 0.75 or greater, 0.8 or greater, 0.85 orgreater, 0.9 or greater or even 1 or greater, and all ranges andsub-ranges therebetween. The amount of Cu and the ratio of Cu¹⁺ ions tototal Cu may be determined by inductively coupled plasma (ICP)techniques known in the art.

In some embodiments, the glass may exhibit a greater amount of Cu¹⁺and/or Cu⁰ than Cu²⁺. For example, based on the total amount of Cu¹⁺,Cu²⁺ and Cu⁰ in the glasses, the percentage of Cu¹⁺ and Cu⁰ combined,may be in the range from about 50% to about 99.9%, from about 50% toabout 99%, from about 50% to about 95%, from about 50% to about 90%,from about 55% to about 99.9%, from about 60% to about 99.9%, from about65% to about 99.9%, from about 70% to about 99.9%, from about 75% toabout 99.9%, from about 80% to about 99.9%, from about 85% to about99.9%, from about 90% to about 99.9%, from about 95% to about 99.9%, andall ranges and sub-ranges therebetween. The relative amounts of Cu¹⁺,Cu²⁺ and Cu⁰ may be determined using x-ray photoluminescencespectroscopy (XPS) techniques known in the art. The tables below reportthese amounts as measured by XPS. Specifically, the tables report theamount of Cu²⁺ and the combination of Cu¹⁺ and Cu⁰. Without being boundby theory, it is believed that most of the embodiments shown in Table 1show copper as being present in the form of Cu¹⁺, under the conditionsthe XPS was performed.

The antimicrobial glass comprises at least a first phase and secondphase. In one or more embodiments, the antimicrobial glass may includetwo or more phases wherein the phases differ based on the ability of theatomic bonds in the given phase to withstand interaction with aleachate. Specifically, the glass of one or more embodiments may includea first phase that may be described as a degradable phase and a secondphase that may be described as a durable phase. The phrases “firstphase” and “degradable phase” may be used interchangeably. The phrases“second phase” and “durable phase” may be used interchangeably. As usedherein, the term “durable” refers to the tendency of the atomic bonds ofthe durable phase to remain intact during and after interaction with aleachate. As used herein, the term “degradable” refers to the tendencyof the atomic bonds of the degradable phase to break during and afterinteraction with one or more leachates. In one or more embodiments, thedurable phase includes SiO₂ and the degradable phase includes at leastone of B₂O₃, P₂O₅ and R₂O (where R can include any one or more of K, Na,Li, Rb, and Cs). Without being bound by theory, it is believed that thecomponents of the degradable phase (i.e., B₂O₃, P₂O₅ and/or R₂O) morereadily interact with a leachate and the bonds between these componentsto one another and to other components in the antimicrobial glass morereadily break during and after the interaction with the leachate.Leachates may include water, acids or other similar materials. In one ormore embodiments, the degradable phase withstands degradation for 1 weekor longer, 1 month or longer, 3 months or longer, or even 6 months orlonger. In some embodiments, longevity may be characterized asmaintaining antimicrobial efficacy over a specific period of time.

In one or more embodiments, the durable phase is present in an amount byweight that is greater than the amount of the degradable phase. In someinstances, the degradable phase forms islands and the durable phaseforms the sea surrounding the islands (i.e., the durable phase). In oneor more embodiments, either one or both of the durable phase and thedegradable phase may include cuprite. The cuprite in such embodimentsmay be dispersed in the respective phase or in both phases.

In some embodiments, phase separation occurs without any additional heattreatment of the antimicrobial glass. In some embodiments, phaseseparation may occur during melting and may be present when the glasscomposition is melted at temperatures up to and including about 1600° C.or 1650° C. When the glass is cooled, the phase separation ismaintained.

The antimicrobial glass may be provided as a sheet or may have anothershape such as particulate, fibrous, and the like. In one or moreembodiments, as shown in FIGS. 1 and 2, the antimicrobial glass 100includes a surface 101 and a surface portion 120 extending from thesurface 101 into the antimicrobial glass at a depth of about 5nanometers (nm) or less. The surface portion may include a plurality ofcopper ions wherein at least 75% of the plurality of copper ionsincludes Cu¹⁺ ions. For example, in some instances, at least about 80%,at least about 85%, at least about 90%, at least about 95%, at leastabout 98%, at least about 99% or at least about 99.9% of the pluralityof copper ions in the surface portion includes Cu¹⁺ ions. yin someembodiments, 25% or less (e.g., 20% or less, 15% or less, 12% or less,10% or less, or 8% or less) of the plurality of copper ions in thesurface portion include Cu²⁺ ions. For example, in some instances, 20%or less, 15% or less, 10% or less, 5% or less, 2% or less, 1% or less,0.5% or less, or 0.01% or less of the plurality of copper ions in thesurface portion include Cu²⁺ ions. In some embodiments, the surfaceconcentration of Cu¹⁺ ions in the antimicrobial glass is controlled. Insome instances, a Cu¹⁺ ion concentration of about 4 ppm or greater canbe provided on the surface of the antimicrobial glass.

The antimicrobial glass of one or more embodiments may a 2 log reductionor greater (e.g., 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5 and all ranges andsub-ranges therebetween) in a concentration of at least one ofStaphylococcus aureus, Enterobacter aerogenes, Pseudomomas aeruginosa,Methicillin Resistant Staphylococcus aureus, and E. coli, under the EPATest. In some instances, the antimicrobial glass exhibits at least a 4log reduction, a 5 log reduction or even a 6 log reduction in theconcentration of at least one of Staphylococcus aureus, Enterobacteraerogenes, Pseudomomas aeruginosa bacteria, Methicillin ResistantStaphylococcus aureus, and E. coli under the EPA Test.

The glasses described herein according to one or more embodiments mayexhibit a 4 log reduction or greater (e.g., 5 log reduction or greater)in a concentration of at least one of Staphylococcus aureus,Enterobacter aerogenes, Pseudomomas aeruginosa bacteria, MethicillinResistant Staphylococcus aureus, and E. coli, under JIS Z 2801 (2000)testing conditions. One or more embodiments of the glasses describedherein also exhibit a 4 log reduction or greater (e.g., 5 log reductionor greater) in a concentration of at least one of Staphylococcus aureus,Enterobacter aerogenes, Pseudomomas aeruginosa, Methicillin ResistantStaphylococcus aureus, and E. coli, under the Modified JIS Z 2801 Testfor Bacterial. As used herein, Modified JIS Z 2801 Test for Bacteriaincludes evaluating the bacteria under the standard JIS Z 2801 (2000)test with modified conditions comprising heating the glass or article toa temperature of about 23 degrees Celsius to about 37 degrees Celsius ata humidity of about 38 percent to about 42 percent for about 6 hours.

In one or more embodiments described herein, the antimicrobial glassesexhibit a 2 log reduction or greater, a 3 log reduction or greater, a 4log reduction or greater, or a 5 log reduction or greater in MurineNorovirus under a Modified JIS Z 2801 for Viruses test. The Modified JISZ 2801 (2000) Test for Viruses includes the following procedure. Foreach material (e.g., the articles or glass of one or more embodiments,control materials, and any comparative glasses or articles) to betested, three samples of the material (contained in individual sterilepetri dishes) are each inoculated with a 20 μL aliquot of a test virus(where antimicrobial activity is measured) or a test medium including anorganic soil load of 5% fetal bovine serum with or without the testvirus (where cytotoxicity is measured). The inoculum is then coveredwith a film and the film is pressed down so the test virus and/or ortest medium spreads over the film, but does not spread past the edge ofthe film. The exposure time begins when each sample was inoculated. Theinoculated samples are transferred to a control chamber set to roomtemperature (about 20° C.) in a relative humidity of 42% for 2 hours.Exposure time with respect to control samples are discussed below.Following the 2-hour exposure time, the film is lifted off using sterileforceps and a 2.00 mL aliquot of the test virus and/or test medium ispipetted individually onto each sample of material and the underside ofthe film (or the side of the film exposed to the sample) used to covereach sample. The surface of each sample is individually scraped with asterile plastic cell scraper to collect the test virus or test medium.The test virus and/or test medium is collected (at 10⁻² dilution), mixedusing a vortex type mixer and serial 10-fold dilutions are prepared. Thedilutions are then assayed for antimicrobial activity and/orcytotoxicity.

To prepare a control sample for testing antimicrobial activity (whichare also referred to as “zero-time virus controls”) for the Modified JISZ 2801 Test for Viruses, three control samples (contained in individualsterile petri dishes) are each inoculated with a 20 μL aliquot of thetest virus. Immediately following inoculation, a 2.00 mL aliquot of testvirus is pipetted onto each control sample. The surface of each samplewas individually scraped with a sterile plastic cell scraper to collecttest virus. The test virus is collected (at 10⁻² dilution), mixed usinga vortex type mixer, and serial 10-fold dilutions were prepared. Thedilutions are assayed for antimicrobial activity.

To prepare controls samples for cytotoxicity (which are also referred toas “2 hour control virus”) for the Modified JIS Z 2801 Test for Viruses,one control sample (contained in an individual sterile petri dish) isinoculated with a 20 μL aliquot of a test medium containing an organicsoil load (5% fetal bovine serum), without the test virus. The inoculumis covered with a film and the film is pressed so the test mediumspreads over the film but does not spread past the edge of the film. Theexposure time begins when each control sample is inoculated. The controlsample is transferred to a controlled chamber set to room temperature(20° C.) in a relative humidity of 42% for a duration of 2 hoursexposure time. Following this exposure time, the film is lifted offusing sterile forceps and a 2.00 mL aliquot of the test medium ispipetted individually onto each control sample and the underside of thefilm (the side exposed to the sample). The surface of each sample isindividually scraped with a sterile plastic cell scraper to collect thetest medium. The test medium is collected (at 10⁻² dilution), mixedusing a vortex type mixer, and serial 10-fold dilutions were prepared.The dilutions were assayed for cytotoxicity.

The antimicrobial glass of one or more embodiments may exhibit the logreduction described herein for long periods of time. In other words, theantimicrobial glass may exhibit extended or prolonged antimicrobialefficacy. For example, in some embodiments, the antimicrobial glass mayexhibit the log reductions described herein under the EPA Test, the JISZ 2801 (2000) testing conditions, the Modified JIS Z 2801 Test forBacteria and/or the Modified JIS Z 2801 Test for Viruses for up to 1month, up to 3 months, up to 6 months, or up to 12 months after theantimicrobial glass is formed or after the antimicrobial glass iscombined with a carrier (e.g., polymers, monomers, binders, solvents andthe like). These time periods may start at or after the antimicrobialglass is formed or combined with a carrier.

One or more embodiments, the antimicrobial glass may exhibit apreservative function, when combined with carriers described herein. Insuch embodiments, the antimicrobial glass may kill or eliminate, orreduce the growth of various foulants in the carrier. Foulants includefungi, bacteria, viruses and combinations thereof.

In one or more embodiments, the glasses and/or articles described hereinleach the copper ions when exposed or in contact with a leachate. In oneor more embodiments, the glass leaches only copper ions when exposed toleachates including water.

In one or more embodiments, the antimicrobial glass and/or articlesdescribed herein may have a tunable antimicrobial activity release. Theantimicrobial activity of the glass and/or articles may be caused bycontact between the antimicrobial glass and a leachate, such as water,where the leachate causes Cu¹⁺ ions to be released from theantimicrobial glass. This action may be described as water solubilityand the water solubility can be tuned to control the release of the Cu¹⁺ions.

In some embodiments, where the Cu¹⁺ ions are disposed in the glassnetwork and/or form atomic bonds with the atoms in the glass network,water or humidity breaks those bonds and the Cu¹⁺ ions available forrelease and may be exposed on the glass or glass ceramic surface.

In one or more embodiments, the antimicrobial glass may be formed usingformed in low cost melting tanks that are typically used for meltingglass compositions such as soda lime silicate. The antimicrobial glassmay be formed into a sheet using forming processes known in the art. Forinstance, example forming methods include float glass processes anddown-draw processes such as fusion draw and slot draw.

The antimicrobial glass may be incorporated into a variety of articles,either alone or in combination with other materials, such as electronicdevices (e.g., mobile phones, smart phones, tablets, video players,information terminal devices, laptop computer, etc.), architecturalstructures (e.g., countertops or walls), appliances (e.g., cooktops,refrigerator and dishwasher doors, etc.), information displays (e.g.,whiteboards), and automotive components (e.g., dashboard panels,windshields, window components, etc.). When used in such articles, theantimicrobial glass can form at least part of the housing and/ordisplay.

After formation, the antimicrobial glass may be formed into sheets andmay be shaped, polished or otherwise processed for a desired end use. Insome instances, the antimicrobial glass may be ground to a powder orparticulate form. In other embodiments, the particulate antimicrobialglass may be combined with other materials or carriers into articles forvarious end uses. The combination of the antimicrobial glass and suchother materials or carriers may be suitable for injection molding,extrusion or coatings or may be drawn into fibers. Such other materialsor carriers may include polymers, monomers, binders, solvents, or acombination thereof as described herein. The polymer used in theembodiments described herein can include a thermoplastic polymer, apolyolefin, a cured polymer, an ultraviolet- or UV-cured polymer, apolymer emulsion, a solvent-based polymer, and combinations thereof.Examples of suitable polymers include, without limitation:thermoplastics including polystyrene (PS), high impact PS, polycarbonate(PC), nylon (sometimes referred to as polyamide (PA)),poly(acrylonitrile-butadiene-styrene) (ABS), PC-ABS blends,polybutyleneterephthlate (PBT) and PBT co-polymers,polyethyleneterephthalate (PET) and PET co-polymers, polyolefins (PO)including polyethylenes (PE), polypropylenes (PP), cyclicpolyolefins(cyclic-PO), modified polyphenylene oxide (mPPO), polyvinylchloride(PVC), acrylic polymers including polymethyl methacrylate (PMMA),thermoplastic elastomers (TPE), thermoplastic urethanes (TPU),polyetherimide (PEI) and blends of these polymers with each other.Suitable injection moldable thermosetting polymers include epoxy,acrylic, styrenic, phenolic, melamine, urethanes, polyesters andsilicone resins. In other embodiments, the polymers may be dissolved ina solvent or dispersed as a separate phase in a solvent and form apolymer emulsion, such as a latex (which is a water emulsion of asynthetic or natural rubber, or plastic obtained by polymerization andused especially in coatings (as paint) and adhesives). Polymers mayinclude fluorinated silanes or other low friction or anti-frictivematerials. The polymers can contain impact modifiers, flame retardants,UV inhibitors, antistatic agents, mold release agents, fillers includingglass, metal or carbon fibers or particles (including spheres), talc,clay or mica and colorants. Specific examples of monomers includecatalyst curable monomers, thermally-curable monomers, radiation-curablemonomers and combinations thereof.

In one example, acrylic latex paint may be combined with 20 wt %antimicrobial glass in particulate form and having a diameter of about 5micrometers (μm). In some embodiments, the resulting combination ofpaint and antimicrobial glass included about 4wt % CuO. In one or moreembodiments, when combined with a carrier such as a polymer, monomer,binder or solvent, the amount of antimicrobial glass may be in the rangefrom about 50 wt % to about 85 wt %. In some embodiments, theantimicrobial glass may be present in an amount in the range from about55 wt % to about 85 wt %, from about 60 wt % to about 85 wt %, fromabout 65 wt % to about 85 wt %, from about 50 wt % to about 80 wt %,from about 50 wt % to about 75 wt %, from about 50 wt % to about 70 wt %and all ranges and sub-ranges therebetween, based on the total weight ofthe antimicrobial glass and carrier. In such embodiments, the totalamount of CuO present in the may be about 20 wt %. In other embodiments,the amount of Cu₂O present in the antimicrobial glass and carriercombination may be in the range from about 10 wt % to about 20 wt % ormore specifically, about 15%. The ratio of antimicrobial glass tocarrier, by vol %, may be in the range from about 90:10 to about 10:90,or more specifically about 50:50.

In one or more embodiments, the antimicrobial glass may be provided inparticulate form and may have a diameter in the range from about 0.1micrometers (μm) to about 10 micrometers (μm), from about 0.1micrometers (μm) to about 9 micrometers (μm), from about 0.1 micrometers(μm) to about 8 micrometers (μm), from about 0.1 micrometers (μm) toabout 7 micrometers (μm), from about 0.1 micrometers (μm) to about 6micrometers (μm), from about 0.5 micrometers (μm) to about 10micrometers (μm), from about 0.75 micrometers (μm) to about 10micrometers (μm), from about 1 micrometers (μm) to about 10 micrometers(μm), from about 2 micrometers (μm) to about 10 micrometers (μm), fromabout 3 micrometers (μm) to about 10 micrometers (μm), from about 3micrometers (μm) to about 6 micrometers (μm), from about 3.5 micrometers(μm) to about 5.5 micrometers (μm), from about 4 micrometers (μm) toabout 5 micrometers (μm), and all ranges and sub-ranges therebetween.The particulate antimicrobial glass may be substantially spherical ormay have an irregular shape. The particles may be provided in a solventand thereafter dispersed in a carrier as otherwise described herein.

Without being bound by theory it is believed that the combination of theantimicrobial glass described herein and a carrier, such as latex paint,provides substantially greater antimicrobial efficacy as compared to thesame latex paint that includes only Cu₂O (cuprite), even when the sameamount of copper is utilized. The presence of Cu¹⁺ crystals in theantimicrobial glasses described herein, even when present as cuprite,tends to remain in the Cu¹⁺ state. Without being bound by theory, it isbelieved that when Cu₂O is provided alone, separate from the glassesdescribed herein, the Cu ions are less stable and may change to Cu²⁺from Cu¹⁺.

The antimicrobial performance of the articles described herein may beimpacted by the presence of a thin layer of polymer on the surface ofthe article. This thin layer may exhibit hydrophobic properties and mayblock the active copper species (Cu¹⁺) from exposure to air or fromleaching to the surface. In one or more embodiments, the articles mayuse polymers that have balanced hydrophobic-hydrophilic properties thatfacilitate leaching of the active copper species. Examples of suchpolymers include hygroscopic/water soluble polymers and surfactants,amphiphilic polymers and/or a combination of amphiphilic polymers andhygroscopic materials. In one or more embodiments, the exposure to airand/or leaching of the active copper species to the surface may befacilitated by providing articles with an exposed treated surface. Inone or more embodiments, the exposed treated surface is a surface thathas been mechanically or chemically treated to expose at least some ofthe glass contained in the article to the air or to provide some of theglass at the surface of the article. Specific methods for providing anexposed treated surface include sanding, polishing, plasma treating(e.g., air, N₂, 0₂, H₂, N₂ and/or Argon based plasma) and other methodsthat will remove a thin layer of the polymer material. In one or morealternative embodiments, the exposed treated surface includes functionalgroups, particularly hydroxyl and carbonyl groups, which are introducedinto or to the exposed treated surface, to make such surface morehydrophilic. By providing an exposed treated surface, the active copperspecies is exposed to air or more readily leaches the surface of thearticle.

To improve processability, mechanical properties and interactionsbetween the polymer and the glass described herein (including anyfillers and/or additives that may be used), processing agents/aids maybe included in the articles described herein. Exemplary processingagents/aids can include solid or liquid materials. The processingagents/aids may provide various extrusion benefits, and may includesilicone based oil, wax and free flowing fluoropolymer. In otherembodiments, the processing agents/aids may includecompatibilizers/coupling agents, e.g., organosilicon compounds such asorgano-silanes/siloxanes that are typically used in processing ofpolymer composites for improving mechanical and themlal properties. Suchcompatibilizers/coupling agents can be used to surface modify the glassand can include (3-acryloxy-propyl)trimethoxysilane;N-(2-aminoethyl)-3-aminopropyltrimethoxysilane;3-aminopropyltri-ethoxysilane; 3-aminopropyltrimethoxysilane;(3-glycidoxypropyl)trimethoxysilane; 3-mercapto-propyltrimethoxysilane;3-methacryloxypropyltrimethoxysilane; and vinyltrimethoxysilane.

In some embodiments, the articles described herein may include fillersincluding pigments, that are typically metal based inorganics can alsobe added for color and other purposes, e.g., aluminum pigments, copperpigments, cobalt pigments, manganese pigments, iron pigments, titaniumpigments, tin pigments, clay earth pigments (naturally formed ironoxides), carbon pigments, antimony pigments, barium pigments, and zincpigments.

After combining the antimicrobial glass described herein with a carrier,as described herein, the combination may be formed into a desiredarticle. Examples of such articles include housings for electronicdevices (e.g., mobile phones, smart phones, tablets, video players,information terminal devices, laptop computer, etc.), architecturalstructures (e.g., countertops or walls), appliances (e.g., cooktops,refrigerator and dishwasher doors, etc.), information displays (e.g.,whiteboards), and automotive components (e.g., dashboard panels,windshields, window components, etc.).

In one or more embodiments, the articles may exhibit desired porosityand may be made into different shapes, including complex shapes and indifferent forms including plastics, rubbers and fiber/fabrics, which canhave the same or different applications. Porous articles can also beused as antimicrobial filters. For example, the articles may be extrudedinto a honeycomb structure, which not only includes channels but alsoporous channel walls.

In other embodiments, the articles may include a high glass loading.Such articles may be formed from a melting process or the wet process.In such embodiments, in addition to using the articles themselves as anantimicrobial material, the polymer can be burnt out or removed toprovide a pure copper glass antimicrobial article that is porous, with asimple or complex shape.

Cu(I) is an excellent catalyst for organic reactions, particularly formild organic reactions, such as polymerization of acrylic monomers andoleochemical applications (e.g., hydrogenolysis of fatty esters to fattyalcohols including both methyl ester and wax ester processes, alkylationof alcohols with amines and amination of fatty alcohols), just to name afew. The articles described herein may be used for such applications.

Examples of the various uses and application of the articles describedherein are shown in FIG. 13.

The articles described herein, including the antimicrobial glass and apolymer, may exhibit a 2 log reduction or greater in a concentration ofat least one of Staphylococcus aureus, Enterobacter aerogenes,Pseudomomas aeruginosa bacteria, Methicillin Resistant Staphylococcusaureus, and E. coli, under the EPA Test. In some instances, the articleexhibits at least a 4 log reduction, a 5 log reduction or even a 6 logreduction in the concentration of at least one of Staphylococcus aureus,Enterobacter aerogenes, Pseudomomas aeruginosa bacteria, MethicillinResistant Staphylococcus aureus, and E. coli under the EPA Test.

The articles described herein according to one or more embodiments mayexhibit a 2 log reduction or greater (e.g., 3 log reduction or greater,4 log reduction or greater, or 5 log reduction or greater) in aconcentration of at least one of Staphylococcus aureus, Enterobacteraerogenes, Pseudomomas aeruginosa bacteria, Methicillin ResistantStaphylococcus aureus, and E. coli, under the JIS Z 2801 (2000) testingconditions and/or the Modified JIS Z 2801 Test for Bacteria. One or moreembodiments of the articles described herein also exhibit a 4 logreduction or greater (e.g., 5 log reduction or greater) in aconcentration of Murine Norovirus (strain MNV-1), under the Modified JISZ 2801 Test for Viruses.

The articles of one or more embodiments may exhibit the log reductiondescribed herein for long periods of time. In other words, the articlemay exhibit extended or prolonged antimicrobial efficacy. For example,in some embodiments, the article may exhibit the log reductions inbacteria and/or viruses described herein for up to 1 month, up to 3months, up to 6 months or up to 12 months after the antimicrobial glassis formed or after the antimicrobial glass is combined with a carrier.These time periods may start at or after the antimicrobial glass isformed or combined with a carrier.

In one or more embodiments, the article may include a coating that maybe applied on a surface, forming a coated surface. The coated surfacemay exhibit a stable color that does not undergo substantial changesafter exposure to specific environments. For example, the coated surfacemay exhibit a delta (Δ) E of less than about 2 or even less than about1, as measured by ASTM D2247, after being exposed to a temperature of38° C. at 100% relative humidity for 7 days. As used herein, the phrase“delta (Δ)E” refers to the total color distance as measured by thedistance between two color coordinates, provided under the CIELAB colorspace (ΔE*_(ab)=√{square root over ((L*₂−L*₁)²+(a*₂−a*₁)²+(b*₂−b*₁)²)}).

The coated surface may also exhibit chemical resistance to variouschemicals, as measured by ASTM D1308, after exposure to chemicals in thecenter of a test piece for 1 hour.

The articles described herein may include pigments to impart color.Accordingly, the coatings made from such articles may exhibit a widevariety of colors, depending on the carrier color, mixture of carriersand amount of particle loading. Moreover, the articles and/or coatingsdescribed herein showed no adverse effect to paint adhesion as measuredby ASTM D4541. In some instances, the adhesion of the article or coatingto an underlying substrate was greater than the cohesive strength of thesubstrate. In other words, in testing, the adhesion between the coatingand the substrate was so strong that the underlying substrate failedbefore the coating was separated from the surface of the substrate. Forexample, where the substrate includes wood, the adhesion between thecoating and the substrate may be about 300 psi or greater, 400 psi orgreater, 500 psi or greater, 600 psi or greater and allranges-sub-ranges therebetween, as measured by ASTM D4541. In someinstances, the article, when applied to a substrate as a coating,exhibits an anti-sag index value of about 3 or greater, about 5 orgreater, 7 or greater, 8 or greater, 9 or greater, 10 or greater, 11 orgreater, 12 or greater, 13 or greater, 14 or greater or even 15 orgreater, as measured by ASTM D4400.

The article and/or coating may exhibit sufficient durability for use inhousehold and commercial applications. Specifically, the article, whenapplied to a substrate as a coating, exhibits a scrub resistance asmeasured by ASTM D4213 of about 4 or greater, 5 or greater, 6 orgreater, 7 or greater and all ranges and sub-ranges therebetween.

In one or more embodiments, the article and/or coating may be resistantto moisture. For example, after exposure of the article and/or coatingto an environment of up to about 95% relative humidity for 24 hours, thearticle and/or coating exhibited no change in antimicrobial activity.

One or more embodiments of the article may include an antimicrobialglass and a carrier with a loading level of the antimicrobial glass suchthat the article exhibits resistance or preservation against thepresence or growth of foulants. Foulants include fungi, bacteria,viruses and combinations thereof. In some instances, the presence orgrowth of foulants in articles, such as paints, varnishes and the like,can cause color changes to the article, can degrade the integrity of thearticle and negatively affect various properties of the article. Byincluding a minimum loading of antimicrobial glass, (e.g., about 5 wt %or less, about 4 wt % or less, about 3 wt % or less, about 2 wt % orless, or about 1 wt % or less) to the carrier, the foulants can beeliminated or reduced. In some instances, the carrier formulation neednot include certain components, when fouling is eliminated or reduced.Thus, the carrier formulations used in one or more embodiments of thearticles described herein may have more flexibility and variations thanpreviously possible, when in known articles that do not include theantimicrobial glass.

Another aspect of this disclosure pertains to a method of making anantimicrobial article. In one or more embodiments, the method includesmelting a glass composition (such as the compositions disclosed herein)to form a glass, forming the glass into particles, fibers or acombination thereof, dispersing the particles and/or fibers into acarrier (e.g., polymer) to provide a filled polymer and forming thefilled polymer into an antimicrobial article.

In one or more embodiments, method includes loading a selected amount ofglass into the polymer, depending on the application of the article.Various methods and processes can be used to such as, for example, an insitu process through mixing monomers with the glass (which may be groundinto particles or other form) and then polymerized (into a thermosettingor a thermoplastic polymer matrix) or by mixing polymer with the glassthrough a process of solution or melt compounding (e.g. using aBrabender compounder or an extruder, single screw or twin screw,reactive or non-reactive), etc.

In one or more embodiments, forming the filled polymer into theantimicrobial article may include extruding or molding the filledpolymer. In one or more embodiments, the antimicrobial article may befurther processed to expose at least a portion of the glass to anexterior surface. The exterior surface may be a surface with which theuser of the antimicrobial article interacts (e.g., the exterior surfaceof a mobile phone, the display of the mobile phone etc.). In one or moreembodiments, the method may include removing a surface portion of theantimicrobial article to expose the glass dispersed in the filledpolymer. Exemplary methods of removing a surface portion of theantimicrobial article may include etching (by plasma, acid or mechanicalmeans such as sanding or polishing).

EXAMPLES

Various embodiments will be further clarified by the following examples.

Examples 1-62

Non-limiting examples of compositions described herein are listed inTable 1. The compositions in Table 1 were batched, melted and formedinto glasses. Table 2 lists selected properties of the compositions ofTable 1 and/or glasses formed therefrom, including the conditions formelting, annealing, appearance of the melt, density, anneal point (asmeasured by Beam Bending Viscometer (BBV)), strain point (as measured byBBV), softening point (as measured by parallel plate viscometer (PPV)),Vickers hardness, Vickers crack initiation, fracture toughness bychevron notch, coefficient of thermal expansion, and other properties.Table 2 also includes the weight percent of Cu oxides, as determined byICP techniques, and the ratio of Cu¹⁺:Cu²⁺ for selected glasses.

Table 3 includes information related to the crystalline phases ofcrystal phase assemblages and/or crystal sizes of selected glasses asdetermined using X-ray diffraction (XRD) techniques known to those inthe art, using such commercially available equipment as the model as aPW1830 (Cu Kα radiation) diffractometer manufactured by Philips,Netherlands. Spectra were typically acquired for 2θ from 5 to 80degrees. Table 3 also includes elemental profile information of selectedglasses determined by XPS techniques.

The glasses where then tested under the EPA test using Staphylococcusaureus under two conditions, as shown in Table 4. Table 4 also includesthe total amount of Cu and Cu¹⁺ found in selected examples, asdetermined by ICP techniques.

TABLE 1 Table 1 Example Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 BatchedComposition (mol %) SiO₂ 65 65 60 60 60 Al₂O₃ 17.5 17.5 20 15 15 CuO17.5 17.5 20 20 20 Na₂O 5 K₂O 5 B₂O₃ P₂O₅ ZnO Batched Composition (wt %)SiO₂ 55.2 55.2 49.8 51.2 50.1 Al₂O₃ 25.2 25.2 28.2 21.7 21.3 CuO 19.719.7 22.0 22.6 22.1 Na₂O 4.4 K₂O 6.5 B₂O₃ P₂O₅ ZnO Example Ex. 6 Ex. 7Ex. 8 Ex. 9 Ex. 10 Batched Composition (mol %) SiO₂ 60 60 60 60 60 Al₂O₃10 10 5 5 CuO 20 20 20 20 20 Na₂O 10 10 5 K₂O 10 5 10 10 B₂O₃ 10 P₂O₅ZnO Batched Composition (wt %) SiO₂ 52.7 50.4 53.0 51.8 52.8 Al₂O₃ 14.914.2 7.5 7.3 0.0 CuO 23.3 22.2 23.4 22.9 23.3 Na₂O 9.1 9.1 4.5 K₂O 13.26.9 13.5 13.8 B₂O₃ 10.2 P₂O₅ ZnO Example Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex.15 Batched Composition (mol %) SiO₂ 60 60 60 50 50 Al₂O₃ 5 CuO 20 20 2020 20 Na₂O K₂O 10 10 10 10 10 B₂O₃ 5 10 P₂O₅ 10 5 5 10 20 ZnO BatchedComposition (wt %) SiO₂ 47.7 49.0 50.1 39.3 35.9 Al₂O₃ 6.9 CuO 21.0 21.622.1 20.8 19.0 Na₂O K₂O 12.5 12.8 13.1 12.3 11.2 B₂O₃ 4.8 9.1 P₂O₅ 18.89.6 9.9 18.5 33.9 ZnO 0.05 MgO 0.05 Fe₂O₃ 0.11 CaO 0.01 Example Ex. 16Ex. 17 Ex. 18 Ex. 19 Ex. 20 Batched Composition (mol %) SiO₂ 50 50 50 5050 Al₂O₃ 25 20 25 25 20 CuO 25 30 25 25 20 Na₂O 5 10 K₂O 5 B₂O₃ P₂O₅ ZnOBatched Composition (wt %) SiO₂ 39.8 40.4 38.3 37.5 41.4 Al₂O₃ 33.8 27.432.5 31.8 28.1 CuO 26.4 32.1 25.3 24.8 21.9 Na₂O 3.9 8.5 K₂O 5.9 B₂O₃P₂O₅ ZnO Example Ex. 21 Ex. 22 Ex. 23 Ex. 24 Ex. 25 Batched Composition(mol %) SiO₂ 50 60 60 50 60 Al₂O₃ 20 5 5 CuO 20 20 20 20 20 Na₂O 10 K₂O10 10 10 10 B₂O₃ 5 10 P₂O₅ 5 5 10 5 ZnO Batched Composition (wt %) SiO₂39.7 49.0 50.1 39.3 51.2 Al₂O₃ 26.9 6.9 7.2 CuO 21.0 21.6 22.1 20.8 22.6Na₂O 8.8 K₂O 12.4 12.8 13.1 12.3 B₂O₃ 4.8 9.1 P₂O₅ 9.6 9.9 18.5 10.1 ZnOExample Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 Batched Composition (mol %)SiO₂ 60 50 50 50 55 Al₂O₃ 5 5 CuO 20 20 20 20 20 Na₂O 10 10 10 K₂O 10 10B₂O₃ 5 10 10 10 10 P₂O₅ 5 10 5 5 5 ZnO Batched Composition (wt %) SiO₂52.5 41.0 42.1 40.3 45.6 Al₂O₃ 7.1 6.8 CuO 23.1 21.7 22.3 21.3 22.0 Na₂O9.0 8.5 8.7 K₂O 12.6 13.0 B₂O₃ 5.1 9.5 9.8 9.3 9.6 P₂O₅ 10.3 19.4 10.09.5 9.8 ZnO Example Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35 BatchedComposition (mol %) SiO₂ 55 60 55 60 55 Al₂O₃ 5 5 CuO 20 20 20 20 20Na₂O 10 15 15 K₂O 10 10 B₂O₃ 10 10 P₂O₅ 5 5 5 5 5 ZnO BatchedComposition (wt %) SiO₂ 47.7 52.7 46.9 49.0 45.6 Al₂O₃ 7.2 6.9 CuO 23.023.3 22.6 21.6 22.0 Na₂O 9.0 13.6 13.2 K₂O 12.8 13.0 B₂O₃ 10.1 9.6 P₂O₅10.3 10.4 10.1 9.6 9.8 ZnO Example Ex. 36 Ex. 37 Ex. 38 Ex. 39 Ex. 40Batched Composition (mol %) SiO₂ 50 45 40 55 55 Al₂O₃ CuO 20 20 20 20 20Na₂O K₂O 10 10 12.5 10 10 B₂O₃ 10 10 10 10 10 P₂O₅ 5 5 5 5 5 ZnO 5 1012.5 Batched Composition (wt %) SiO₂ 40.9 36.3 31.6 45.6 45.6 Al₂O₃ CuO21.6 21.3 20.9 22.0 22.0 Na₂O K₂O 12.8 12.6 15.5 13.0 13.0 B₂O₃ 9.5 9.39.2 9.6 9.6 P₂O₅ 9.7 9.5 9.3 9.8 9.8 ZnO 5.5 10.9 13.4 Example Ex. 41Ex. 42 Ex. 43 Ex. 44 Ex. 45 Batched Composition (mol %) SiO₂ 51.5 51.548 48 55 Al₂O₃ 0 0 0 0 CuO 25 25 30 30 20 Na₂O 0 0 0 0 K₂O 9.4 9.4 8.88.8 10 B₂O₃ 9.4 9.4 8.8 8.8 10 P₂O₅ 4.7 4.7 4.4 4.4 5 ZnO 0 0 0 0 55Batched Composition (wt %) SiO₂ 42.4 42.4 39.3 39.3 Al₂O₃ 0.0 0.0 0.00.0 CuO 27.3 27.3 32.5 32.5 Na₂O 0.0 0.0 0.0 0.0 K₂O 12.1 12.1 11.3 11.3B₂O₃ 9.0 9.0 8.4 8.4 P₂O₅ 9.2 9.2 8.5 8.5 ZnO 0.0 0.0 0.0 0.0 BatchedComposition Example (mol %) Ex. 46 Ex. 47 Ex. 48 Ex. 49 Ex. 50 SiO₂ 5050 50 50 55 Al₂O₃ 0 0 0 0 0 CuO 20 20 20 20 20 Na₂O 0 0 0 0 0 K₂O 10 1010 10 10 B₂O3 10 10 10 10 10 P₂O5 5 5 5 5 5 ZnO 0 0 0 0 0 TiO₂ 5 0 0 0 0Fe₂O₃ 0 5 0 0 0 Cr₂O₃ 0 0 5 0 0 Co₃O₄ 0 0 0 5 0 NiO 0 0 0 0 0 BatchedComposition Example (mol %) Ex. 51 Ex. 52 Ex. 53 Ex. 54 Ex. 55 SiO₂ 4045 50 55 50 Al₂O₃ 15 15 15 15 15 CuO 20 20 20 20 20 Na₂O K₂O 10 10 10 55 B₂O3 10 5 0 0 5 P₂O5 5 5 5 5 5 ZnO 0 0 0 0 0 TiO₂ 0 0 0 0 0 Fe₂O₃ 0 00 0 0 Cr₂O₃ 0 0 0 0 0 Co₃O₄ 0 0 0 0 0 NiO 0 0 0 0 0 Batched CompositionExample (mol %) Ex. 56 Ex. 57 Ex. 58 Ex. 59 Ex. 60 SiO₂ 45 55 50 45 45Al₂O₃ CuO 35 30 35 40 25 Na₂O K₂O 7.5 10 10 10 10 B₂O3 7.5 P₂O5 5 5 5 55 ZnO TiO₂ Fe₂O₃ Cr₂O₃ Co₃O₄ 15 NiO Batched Composition Example (mol %)Ex. 61 Ex. 62 SiO₂ 45 45 Al₂O₃ 0 0 CuO 25 30 Na₂O 0 0 K₂O 10 10 B₂O3 0 0P₂O5 5 5 ZnO 0 0 TiO₂ 0 10 Fe₂O₃ 0 0 Cr₂O₃ 0 0 Co₃O₄ 0 0 NiO 15 0

TABLE 2 Table 2 Example Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Melt Temp (° C.)1500 1650 1650 1650 1650 Melt Time (hrs) 6 overnight overnight overnightovernight Crucible Type Alumina Quartz Quartz Quartz Quartz Anneal Temp(° C.) 700 700 700 700 700 Melt Appearance Very Poor, High Quality, HighQuality, Grey Surface, Grey Surface, full of large Surface Oxidation,Surface Oxidation, black interior black interior bubbles Gray surface,Gray surface, black interior black interior Density by buoyancy 2.7052.781 2.758 2.741 (g/cm³) Effective molecular wt 70.821 70.821 72.354(g/mol) Molar Volume (cm³/mol) 26.2 26.0 Anneal Point by BBV (° C.)694.1 684.9 598.6 Strain Point by BBV (° C.) 652.5 642.3 558.9 SofteningPoint by PPV xstallized xstallized (° C.) Vickers Hardness 595 586(kgf/mm²) Vickers Crack Initiation 1-2 1-2 (kgf) Fracture Toughness0.875 0.887 by Chevron Notch (MPa m^(0.5)) CTE (ppm/° C.) 1.06 1.15 ICPwt % oxides (Cu) 19.6 19 21.6 ratio Cu⁺¹/Cu²⁺ Example Ex. 6 Ex. 7 Ex. 8Ex. 9 Ex. 10 Melt Temp (° C.) 1650 1650 1650 1650 1650 Melt Time (hrs)overnight overnight overnight overnight overnight Crucible Type QuartzQuartz Quartz Quartz Quartz Anneal Temp (° C.) 700 700 700 700 600 MeltAppearance Black and gray Black and gray Black and Grey lustrouslustrous surface, lustrous surface, grey surface, surface, dark brownand brown and primarily black yellow interior yellow interior yellowinterior interior with some green and brown streaks Density by buoyancy2.706 2.666 2.596 2.716 (g/cm³) Effective molecular wt (g/mol) MolarVolume (cm³/mol) Anneal Point by BBV (° C.) 737.2 575.7 Strain Point byBBV (° C.) 684.4 535.2 Softening Point by PPV (° C.) Vickers Hardness(kgf/mm²) Vickers Crack Initiation (kgf) Fracture Toughness by ChevronNotch (MPa m^(0.5)) CTE (ppm/° C.) ICP wt % oxides (Cu) ratio Cu⁺¹/Cu²⁺Example Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Melt Temp (° C.) 1650  16501650 1650 1650  Melt Time (hrs) overnight overnight overnight overnightovernight Crucible Type Quartz Quartz Quartz Quartz Quartz Anneal Temp(° C.) 600 700 600 600 600 Melt Appearance Ceramic, brittle, Shinymetallic Shiny metallic Dark yellow Ceramic, grey gray, brown, surface,dark surface, dark surface w/some surface, light and green yellowinterior yellow interior ceramic, dark brown interior yellow interiorw/some ceramic Density by buoyancy 2.669 2.673 2.608 (g/cm³) Effectivemolecular wt (g/mol) Molar Volume (cm³/mol) Anneal Point by BBV (° C.)Strain Point by BBV (° C.) 701 569 572.5 Softening Point by PPV 759.8602.8 510.7 (° C.) Vickers Hardness (kgf/mm²) Vickers Crack Initiation(kgf) Fracture Toughness by Chevron Notch (MPa m^(0.5)) CTE (ppm/° C.)ICP wt % oxides (Cu) ratio Cu⁺¹/Cu²⁺ Example Ex. 16 Ex. 17 Ex. 18 Ex. 19Ex. 20 Melt Temp (° C.) 1650 1650 1650 1650 1650 Melt Time (hrs)overnight overnight overnight overnight overnight Crucible Type QuartzQuartz Quartz Quartz Quartz Anneal Temp (° C.) 700 700 700 700 700 MeltAppearance Grey Surface, Grey Surface, Grey Surface, Grey Surface, GreySurface, black interior, black interior black interior black interiorblack interior copper precipitated Density by buoyancy 2.91 2.901 2.8872.876 2.797 (g/cm³) Effective molecular wt (g/mol) Molar Volume(cm³/mol) Anneal Point by BBV (° C.) Strain Point by BBV (° C.)Softening Point by PPV (° C.) Vickers Hardness (kgf/mm²) Vickers CrackInitiation (kgf) Fracture Toughness by Chevron Notch (MPa m^(0.5)) CTE(ppm/° C.) ICP wt % oxides (Cu) ratio Cu⁺¹/Cu²⁺ Example Ex. 21 Ex. 22Ex. 23 Ex. 24 Ex. 25 Melt Temp (° C.) 1650 1650  1650  1650  1650  MeltTime (hrs) Overnight overnight overnight Overnight overnight CrucibleType Quartz Quartz Quartz Quartz Quartz Anneal Temp (° C.) 700 650 650650 650 Melt Appearance Grey Surface, Grey Surface, Grey Surface,Crystallized Grey Surface, yellow interior Yellow/orange Yellow/orangeYellow/orange interior interior interior (looks more crystalline thanEx. 22) Density by buoyancy 2.774 (g/cm³) Effective molecular wt (g/mol)Molar Volume (cm³/mol) Anneal Point by BBV (° C.) Strain Point by BBV (°C.) Softening Point by PPV (° C.) Vickers Hardness (kgf/mm²) VickersCrack Initiation (kgf) Fracture Toughness by Chevron Notch (MPa m^(0.5))CTE (ppm/° C.) ICP wt % oxides (Cu) ratio Cu⁺¹/Cu²⁺ Example Ex. 26 Ex.27 Ex. 28 Ex. 29 Ex. 30 Melt Temp (° C.) 1650  1650  1650  1650  1650Melt Time (hrs) overnight overnight overnight overnight overnightCrucible Type Quartz Quartz Quartz Quartz Quartz Anneal Temp (° C.) 650650 650 650 650 Melt Appearance Grey Surface, crystallized Shinyexterior, Shiny exterior, Shiny exterior, Yellow/orange yellow/orangeyellow/orange yellow/orange interior interior interior interior (looksmore crystalline than Ex. 23) Density by buoyancy 2.626 (g/cm³)Effective molecular wt (g/mol) Molar Volume (cm³/mol) Anneal Point byBBV (° C.) Strain Point by BBV (° C.) 602.4 Softening Point by PPV 544.4(° C.) Vickers Hardness (kgf/mm²) Vickers Crack Initiation (kgf)Fracture Toughness by Chevron Notch (MPa m^(0.5)) CTE (ppm/° C.) ICP wt% oxides (Cu) ratio Cu⁺¹/Cu²⁺ Example Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35Melt Temp (° C.) 1650  1650  1650  1650  1650  Melt Time (hrs) overnightovernight overnight overnight overnight Crucible Type Quartz QuartzQuartz Quartz Quartz Anneal Temp (° C.) 650 650 650 650 650 MeltAppearance Shiny exterior, Lighter yellow, Lighter yellow, OrangeInterior, Orange Interior, yellow/orange more crystalline crystallizedshiny metallic shiny metallic interior surface surface Density bybuoyancy (g/cm³) Effective molecular wt (g/mol) Molar Volume (cm³/mol)Anneal Point by BBV (° C.) Strain Point by BBV (° C.) Softening Point byPPV (° C.) Vickers Hardness (kgf/mm²) Vickers Crack Initiation (kgf)Fracture Toughness by Chevron Notch (MPa m^(0.5)) CTE (ppm/° C.) ICP wt% oxides (Cu) ratio Cu⁺¹/Cu²⁺ Example Ex. 36 Ex. 37 Ex. 38 Ex. 39 Ex. 40Melt Temp (° C.) 1650  1650  1650  1650 1650  Melt Time (hrs) overnightovernight overnight overnight overnight Crucible Type Quartz QuartzQuartz Quartz Quartz Anneal Temp (° C.) 650 650 650 none 650 MeltAppearance Orange Interior, Orange Interior, Orange Interior, Yellow,Orange Orange Interior, shiny metallic shiny metallic shiny metallicshiny metallic surface surface surface surface Density by buoyancy(g/cm³) Effective molecular wt (g/mol) Molar Volume (cm³/mol) AnnealPoint by BBV (° C.) Strain Point by BBV (° C.) Softening Point by PPV (°C.) Vickers Hardness (kgf/mm²) Vickers Crack Initiation (kgf) FractureToughness by Chevron Notch (MPa m^(0.5)) CTE (ppm/° C.) ICP wt % oxides(Cu) ratio Cu⁺¹/Cu²⁺ Example Ex. 41 Ex. 42 Ex. 43 Ex. 44 Melt Temp (°C.) 1650 1650  1650 1650  Melt Time (hrs) overnight overnight overnightovernight Crucible Type Quartz Quartz Quartz Quartz Anneal Temp (° C.)none 650 none 650 Melt Appearance Yellow, Orange Orange Interior,Yellow, Orange Orange Interior, shiny metallic shiny metallic surfacesurface Density by buoyancy 2.816 (g/cm³) Effective molecular wt (g/mol)Molar Volume (cm³/mol) Anneal Point by BBV (° C.) Strain Point by BBV (°C.) Softening Point by PPV (° C.) Vickers Hardness (kgf/mm²) VickersCrack Initiation (kgf) Fracture Toughness by Chevron Notch (MPa m^(0.5))CTE (ppm/° C.) ICP wt % oxides (Cu) ratio Cu⁺¹/Cu²⁺ Example Ex. 46 Ex.47 Ex. 48 Ex. 49 Ex. 50 Melt Temp (° C.) Melt Time (hrs) Crucible TypeAnneal Temp (° C.) Melt Appearance reddish orange orange greenish lightgreen, crystallized greener than Ex. 48 Density by buoyancy (g/cm³)Effective molecular wt (g/mol) Molar Volume (cm³/mol) Anneal Point byBBV (° C.) Strain Point by BBV (° C.) Softening Point by PPV (° C.)Vickers Hardness (kgf/mm²) Vickers Crack Initiation (kgf) FractureToughness by Chevron Notch (MPa m^(0.5)) CTE (ppm/° C.) ICP wt % oxides(Cu) ratio Cu⁺¹/Cu²⁺ Example Ex. 51 Ex. 52 Ex. 53 Ex. 54 Ex. 55 Ex. 56Melt Temp (° C.) Melt Time (hrs) Crucible Type Anneal Temp (° C.) MeltAppearance Yellow and Yellow and Yellow Black with Black withPumpkin-colored Black Brown some orange some orange on bottom on edgesDensity by buoyancy (g/cm³) Effective molecular wt (g/mol) Molar Volume(cm³/mol) Anneal Point by BBV (° C.) Strain Point by BBV (° C.)Softening Point by PPV (° C.) Vickers Hardness (kgf/mm²) Vickers CrackInitiation (kgf) Fracture Toughness by Chevron Notch (MPa m^(0.5)) CTE(ppm/° C.) ICP wt % oxides (Cu) ratio Cu⁺¹/Cu²⁺ *The term “crystallized”as used here refers to a non-glassy appearance.

TABLE 3 Table 3 Example Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 XRD powder noneTenorite Tenorite (CuO) (CuO) XRD surface Tenorite Tenorite (CuO) (CuO)XPS vacuum fracture + 2 min air % Cu¹⁺ and Cu⁰ 85.2 % Cu²⁺ 14.8 StDev 1XPS vacuum fracture % Cu¹⁺ and Cu⁰ % Cu²⁺ StDev Example Ex. 6 Ex. 7 Ex.8 Ex. 9 Ex. 10 XRD powder Tenorite Tenorite Cuprite Cuprite (CuO) and(CuO) and (Cu₂O) (Cu₂O) Cuprite Cuprite (Cu₂O) (Cu₂O) XRD surfaceTenorite Tenorite no peaks Tenorite (CuO) and (CuO) and (CuO) andCuprite Cuprite Cuprite (Cu₂O) (Cu₂O) (Cu₂O) XPS vacuum fracture + 2 minair % Cu¹⁺ and Cu⁰ 84.2 74.6 % Cu²⁺ 15.8 25.4 StDev 0.1 1.5 XPS vacuumfracture % Cu¹⁺ and Cu⁰ % Cu²⁺ StDev Example Ex. 11 Ex. 12 Ex. 13 Ex. 14Ex. 15 XRD powder Cuprite (Cu₂O), Cuprite Cuprite K1-xAl¹⁺xSi1-xO4,(Cu2O) (Cu₂O) Al2O3*0.95P2O5, Cu1.82K0.2(Al3.9Si8.1O24), K2SiO3 XRDsurface Tenorite (CuO), Cuprite Cuprite Cuprite (CU₂O),K1-xAl¹⁺xSi1-xO4, (Cu₂O) (Cu₂O) Al2O3*0.95P2O5 XPS vacuum fracture + 2min air % Cu¹⁺ and Cu⁰ 92.4 80.3 91.3 % Cu²⁺ 7.6 19.7 8.7 StDev 1.2 2.50.4 XPS vacuum fracture % Cu¹⁺ and Cu⁰ 87.1 93.1 % Cu²⁺ 12.9 6.9 StDev2.6 0.6 Example Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 XRD powder TenoriteTenorite Tenorite none Tenorite (CuO) (CuO) (CuO) (CuO) XRD surfaceTenorite Tenorite Tenorite Tenorite Tenorite (CuO) (CuO) (CuO) (CuO)(CuO) XPS vacuum fracture + 2 min air % Cu¹⁺ and Cu⁰ % Cu²⁺ StDev XPSvacuum fracture % Cu¹⁺ Cu⁰ % Cu²⁺ StDev Example Ex. 21 Ex. 22 Ex. 23 Ex.24 Ex. 25 XRD powder Cuprite Cuprite, Tenorite, Cuprite Cristobalite,Cuprite, (Cu₂O) Sodium Borate Copper Sodium Silicate (Na₂B₁₈O₂₈),(Na₂Si₂O₅), Potassium Aluminum Aluminum Phosphate Silicate (KAlSiO₄)(AlPO₄) XRD surface Tenorite Cuprite, Tenorite, Cuprite, Tenorite,Cuprite Cuprite, Tenorite, (CuO) Sodium Borate Sodium Borate SodiumSilicate (Na₂Si₂O₅), Aluminum Phosphate (AlPO₄) XPS vacuum fracture + 2min air % Cu¹⁺ and Cu⁰ 81.7 % Cu²⁺ 18.3 StDev 0.2 XPS vacuum fracture %Cu¹⁺ and Cu⁰ % Cu²⁺ StDev Example Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 XRDpowder Cristobalite, Cuprite, Copper, Cuprite, Cuprite Cuprite CupriteCopper Phosphate Sodium Copper (Cu₃(PO₄)₂ Phosphate (Na₆Cu₉(PO₄)₆) XRDsurface Cristobalite, Cuprite, Copper, Cuprite, Cuprite, Sodium CupriteCuprite, Tenorite Tenorite, Copper Tenorite, Sodium Borate HydratePhosphate Copper Phosphate XPS vacuum fracture + 2 min air % Cu¹⁺and Cu⁰87.1 75 % Cu²⁺ 12.9 25 StDev 1.2 0.2 XPS vacuum fracture % Cu¹⁺ and Cu⁰% Cu²⁺ StDev Example Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35 XRD powderCuprite Cristobalite, Cuprite, Cuprite, Sodium Phosphate SodiumPhosphate, (Na₃PO₄), AluminumNa_(0.24)H_(4.9)((Al_(5.14)Si_(48.86))O₁₀₆)(H₂O)_(26.5) PhosphateHydrate (AlPO₄*xH₂O), Copper Phosphate (Cu₅P₂O₁₀) XRD surface Cuprite,Tenorite, Cristobalite, Tenorite, Tenorite, Sodium Tincalconite(Na₂B₄O₇*5H₂O), Sodium Phosphate Phosphate, Cuprite Copper Phosphate(Na₃PO₄), Aluminum Hydrate Cu₃(PO₃)₆*14H₂O Phosphate Hydrate(AlPO₄*xH₂O), Copper Phosphate (Cu₅P₂O₁₀) XPS vacuum fracture + 2 minair % Cu¹⁺ and Cu⁰ 68.7 % Cu²⁺ 31.3 StDev 0.6 XPS vacuum fracture % Cu¹⁺and Cu⁰ % Cu²⁺ StDev Example Ex. 36 Ex. 37 Ex. 38 Ex. 39 Ex. 40 XRDpowder Cuprite, Potassium Cuprite, Potassium Cuprite, Potassium CupriteCuprite Zinc Phosphate Zinc Phosphate, Zinc Phosphate (KZnPO₄) PotassiumZinc (KZnPO₄), Potassium Silicate (K_(1.10)Zn_(0.55)Si_(1.45)O₄), ZincSilicate, Potassium Zinc Potassium Zinc Phosphate (K₆Zn(P₂O₇)₂ PhosphateXRD surface Cuprite, Potassium Tenorite, Copper Tenorite, Potassium ZincPhosphate Zinc Phosphate Zinc Phosphate, (KZnPO₄), Copper (CuZn(P₂O₇),Potassium Potassium Zinc Silicon Phosphide Phosphate (K₄(P₂O₈),Silicate, Potassium (Cu_(0.56)Si_(1.44))P₂, Tenorite Aluminum PhosphateCopper Oxide (AlPO₄) (K₃CuO₄), Cuprite, Copper Oxide Phosphate(Cu₄O(PO₄)₂ XPS vacuum fracture + 2 min air % Cu¹⁺ and Cu⁰ % Cu²⁺ StDevXPS vacuum fracture % Cu¹⁺ and Cu⁰ % Cu²⁺ StDev Example Ex. 41 Ex. 42Ex. 43 Ex. 44 Ex. 45 XRD powder Cuprite Cuprite Cuprite Cuprite XRDsurface XPS vacuum fracture + 2 min air % Cu¹⁺ Cu0 % Cu²⁺ StDev XPSvacuum fracture % Cu¹⁺ Cu0 % Cu²⁺ StDev Example Ex. 46 Ex. 47 Ex. 48 Ex.49 Ex. 50 XRD powder Cuprite, Copper Cuprite Titanium Oxide, Anatase XRDsurface Cuprite, Copper Titanium Oxide, Anatase XPS vacuum fracture + 2min air % Cu¹⁺ Cu0 % Cu²⁺ StDev XPS vacuum fracture % Cu¹⁺ Cu0 % Cu²⁺StDev Example Ex. 51 Ex. 52 Ex. 53 Ex. 54 Ex. 55 XRD powder CupriteTenorite and cuprite tenorite and tenorite and cuprite cuprite cupriteXRD surface Tenorite and Tenorite and Tenorite and tenorite tenoritecuprite cuprite cuprite XPS vacuum fracture + 2 min air % Cu¹⁺ Cu0 %Cu²⁺ StDev XPS vacuum fracture % Cu¹⁺ Cu0 % Cu²⁺ StDev Example Ex. 56XRD powder Cuprite and copper potassium oxide XRD surface cuprite andtenorite and potassium borate XPS vacuum fracture + 2 min air % Cu¹⁺ Cu0% Cu²⁺ StDev XPS vacuum fracture % Cu¹⁺ Cu0 % Cu²⁺ StDev

TABLE 4 Table 4 Example Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Coupon Testing As-<log 1 <log 1 <log 1 <log 1 Received EPA Test (S. Aureus) Coupon TestingAs- <log 1 Received EPA Re- Test Coupon Testing 1 Day 85° C./85% RH EPATest ICP Total Cu in wt % 21.6 21.7 ICP Cu⁺¹/total Cu 0.86 0.87 0.88Example Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Coupon Testing As- >log 3 log2.84 <log 1 <log 1 Received EPA Test (S. Aureus) Coupon Testing As- >log1 <log 1 <log 1 Received EPA Re- Test Coupon Testing 1 Day 85° C./85% RHEPA Test ICP Total Cu in wt % 19.6 15.8 22 ICP Cu⁺¹/total Cu 0.88 0.860.78 0.8 Example Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Coupon TestingAs- >log 4 >log 3 >log 6 Received EPA Test (S. Aureus) Coupon TestingAs- >log 3 >log 4 Received EPA Re- Test Coupon Testing 1 Day 85° C./85%RH EPA Test ICP Total Cu in wt % 20.8 20.8 20.5 ICP Cu⁺¹/total Cu 0.850.77 0.85 Example Ex. 21 Ex. 22 Ex. 23 Ex. 24 Ex. 25 Coupon Testing As-<log 1 <log 1 >log 4 Received EPA Test (S. Aureus) Coupon Testing As-Received EPA Re- Test Coupon Testing 1 <log 1 <log 1 <log 1 Day 85°C./85% RH EPA Test ICP Total Cu in wt % 18.1 21.5 21.9 21.5 ICPCu⁺¹/total Cu 0.92 0.8 0.8 0.85 Example Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex.30 Coupon Testing As- >log 3 >log 3 >log 4 Received EPA Test (S. Aureus)Coupon Testing As- Received EPA Re- Test Coupon Testing 1 >log2 >log2 >log 4 Day 85° C./85% RH EPA Test ICP Total Cu in wt % 21.3 21.422.2 21.6 ICP Cu⁺¹/total Cu 0.75 0.82 0.89 0.86 Example Ex. 31 Ex. 32Ex. 33 Ex. 34 Ex. 35 Coupon Testing As- >log 3 Received EPA Test (S.Aureus) Coupon Testing As- Received EPA Re- Test Coupon Testing 1 >log 2Day 85° C./85% RH EPA Test ICP Total Cu in wt % 22.4 19.8 19.1 ICPCu⁺¹/total Cu 0.86 0.77 0.85 Example Ex. 41 Ex. 42 Ex. 43 Ex. 44 CouponTesting As- >log 6 log 5.93 Received EPA Test (S. Aureus) Coupon TestingAs- Received EPA Re- Test Coupon Testing 1 Day 85° C./85% RH EPA TestICP Total Cu in wt % ICP Cu⁺¹/total Cu 0.88 Example Ex. 46 Ex. 49 Ex. 56Ex. 58 Coupon Testing As- 0.53 1.42 6.151 6.151 Received EPA Test (S.Aureus) Coupon Testing As- Received EPA Re- Test Coupon Testing 1 Day85° C./85% RH EPA Test ICP Total Cu in wt % ICP Cu⁺¹/total Cu

Regarding Example 13, SEM images indicate that phase separation occurredand included a glassy matrix phase and a dispersed glassy second phase.The dispersed phase is considered a degradable phase and includedcuprite crystals. The degradation of the dispersed phase was evidentwhen that phase partially dissolved when the formed glass was polishedin water. EDS analysis showed a glassy phase enriched in silicon (i.e.,a durable phase) relative to both the glassy second phase andcrystalline phase. The crystalline phase was the most copper-rich.Without being bound by theory, it is believed that the glassy secondphase is enriched in boron. The phase separation of the degradable phase(including the precipitation of cuprite crystals) occurred readilywithout additional heat treatment beyond simple post-melt annealing.

FIGS. 3-5 are TEM and SEM images of a glasses made from the compositionof Example 30. FIG. 3 shows a TEM image in which the darkest areasindicate a silica-rich glassy phase and the lighter areas arephase-separated glassy regions enriched with phosphorus, boron andpotassium. As discussed above, these phase-separated glassy regions aredegradable regions, and the silica-rich glassy phase is a durable phase.Both the degradable phase and durable phase form the glass phase of theglass. The lightest areas shown in the TEM image of FIG. 3 indicatecuprite crystals. The areas that are appear darker than the lightestareas indicate phase-separated glassy regions enriched with phosphorus,boron and potassium (i.e., the degradable phase). The silica-rich glassyphase is indicated by the darkest regions in FIG. 3. Facets of thecuprite crystals can be seen in the TEM image of FIG. 3. FIG. 4 shows aSEM image of a cross-section of the glass, after polishing with water.From FIG. 4, a preferential dissolution of a degradable phase (i.e., thephase-separated glassy regions enriched with phosphorus, boron andpotassium shown in FIG. 3) in water can be seen. The Cu¹⁺ ions containedin the cuprite crystals that form the degradable phase are released bythe dissolution of the degradable phase.

FIG. 6 shows an STEM image of the glasses made from the compositionsdescribed herein. FIG. 6 shows a three-phase morphology in which copperis present in a particulate form and wrapped by phosphate anddistributed in a glass matrix. Because the phosphate is lightly solublein water and hence it will be dissolved by water, exposing the Cuparticles that will release active Cu species to function (killingviruses and bacteria).

Phase separation of the glass upon melting is shown in FIGS. 7A-7B and8A-8B, which are EDX hypermaps of cross-section TEM images of sampleslifted from bulk and surface areas. The same magnification was used toin both TEM images. FIGS. 7 A-7B show the bulk and surface areas,respectively, of Example 30 immediately after melting at 1650° C. andannealing at 650° C. versus quenching in water from the 1650° C. melttemperature. FIG. 7A, which shows the quenched sample, is phaseseparated and includes cuprite crystals within a degradable phase.Accordingly, the phase separation and formation of crystals was notsuppressed by quenching. Accordingly, FIG. 7A shows phase separationoccurs at 1600° C. or in the melt. Specifically, FIG. 7A shows a durablephase as the darkest color, the lightest parts indicate the presence ofcopper and parts surrounding the lightest parts and having a slightlydarker color represents phosphorus. FIGS. 8A-8B show SEM images of afracture cross-section and a polished cross-section, respectively, ofExample 30 following an additional heat treatment at 800° C. for 1 hour.The additional heat treatment appears to have ripened themicrostructure. The size of largest cuprite crystals increased and thenumber of nanoscale bright contrast phases is significantly reduced whencompared to samples prepared by a standard method, as shown in FIGS. 4and 5. In some embodiments, the concentration of copper exceeds thesolubility limit in the degradable phase and the copper precipitates outof the degradable phase. Accordingly, the antimicrobial glass hasantimicrobial activity in the molten state and when cooled into thefinished state, without any additional heat treatment (e.g., heattreatment in hydrogen at temperatures up to about 600° C.). Theantimicrobial glass includes Cu¹⁺ and/or Cu⁰ in sufficient amounts andpresent in the degradable phase, that copper ions are leached out andprovide antimicrobial efficacy.

The release of the Cu¹⁺ ions provides the antimicrobial activity, asdemonstrated in the log reduction of Staphylococcus aureus under the EPATest when the glass was tested as-received and after 1 day under theconditions listed in Table 4.

The antimicrobial performance of the glasses described herein was testedby forming a coupon or substrate article having dimensions of 2.5 cm×2.5cm.

To test the antimicrobial activity of the examples, the EPA Test wasutilized. In the examples described herein, Staphylococcus aureus (ATCC6538) was cultured for 5 consecutive days before the testing wasperformed. Bacterial culture was mixed with serum (5% finalconcentration) and Triton X-100 (final concentration 0.01%). Eachsample/carrier was inoculated with 20 ul of the bacterial suspension andallowed to dry (typically, for about 20 minutes to 40 minutes) at roomtemperature and 42% relative humidity prior to being exposed tobacterial for a 2 hour exposure period. After 2 hours of exposure,bacteria are washed from the carrier using neutralizer buffer and platedonto Tryptic soy agar plates. Twenty-four hours after incubation at 37°C., bacteria colony formation was examined and counted. Geometric meanand percent reduction were calculated based on the colony number fromsamples relative to glass carrier or appropriate paint control.

The articles according to one or more embodiments were formed asfollows. The glass was ground into a powder and mixed with acommercially available carrier described as a clear gloss protectivefinish, available under the trademark Polycrylic® from Minwax Company.The copper loading (wt %/wt %) was either about 5%, 10% or 15%(calculated on the basis that the glass includes about 20 wt % Cu). Themixed carrier and glass powder was then brush coated onto Pyvek® paperthat was backed with a polymer film, before being coated. The coatedPyvek® paper was cut into 2.5×2.5 cm coupons for the antimicrobialperformance testing.

Where a thermoplastic polymer was utilized, the glass powder wascompounded with a commercially available polymer, having the trademarkPeralthane®, at a temperature in the range from between 195 ° C. -220°C. and a rate of 50 rpm. The loading of the glass was at about 60-80%.The resulting polymer and glass composite was made into 2.5×2.5 cmcoupons by a hot press process.

In some examples, an epoxy resin was utilized. In such examples, about3.0 g of a commercially available epoxy resin, Erisys GE22, was combinedwith about 1 g of a curing agent, Amicure PACM and 2 g of ethanol in a20 mL vial, and mixed well. About 10 g of the powdered glass was addedand mixed well. The resulting mixture was cured at room temperature fora few days and then the vial was broken to gel the combination, whichwas further dried at room temperature for one day and at 65° C. forseveral hours. This results in dried epoxy resin/glass composite.

The examples that were combined with an epoxy resin were also tested todetermine the density or porosity of the composite. This includedplacing the example in water for 2 minutes and then removing theexample. The mass difference before and after placement in the water wasmeasured to demonstrate the porosity of the example.

Coupons made entirely of the glasses of Examples 4, 5, 6, 9, 10, 12, 13,14 and 21 were tested under the EPA Test. In addition, a ComparativeSubstrate of pure copper metal was also tested under the EPA Test. FIG.9 illustrates the antimicrobial performance of those glasses. Example 14exhibited at least the same antimicrobial performance as the ComparativeSubstrate, with Examples 6, 12 and 13 exhibiting greater than 3 logreduction in Staphylococcus aureus.

Glass 56 was formed into particles having an average major dimension ofabout 1 μm or less. The particles were combined with a polymer carrier.The loading of the particles in the carrier was about 5%. Theantimicrobial efficacy, as measured by the EPA test for S. aureus wasevaluated immediately after the combination of the particles and thepolymer carrier, one week after combination of the particles and thepolymer carrier, one month after combination of the particles and thepolymer carrier and three months after combination of the particles andthe polymer carrier. FIG. 10 is a graph showing the antimicrobialefficacy after each period of time. As shown in FIG. 10, the glassexhibits at least a 2 log reduction in S. aureus even at three monthsafter being formed into particles and combined with a polymer carrier.In addition, the combination of the glass particles and the polymercarrier exhibited greater than 5 log reduction at one month aftercombination.

Glass 56 and a Comparative Glass (A) (including 10% by weight silver ioncontent diffused therein) were evaluated for antimicrobial activity withrespect to Murine Norovirus and cytotoxicity, under the Modified JIS Z2801 Test for Viruses. Antimicrobial activity control samples andcytotoxicity control samples of Glass 56 and Comparative Glass A werealso prepared, as described per the Modified JIS Z 2801 Test forViruses. Table 5 shows the input virus control and the antimicrobialactivity control results, Table 6 shows the cytotoxicity controlresults, Table 7 shows the results of Comparative Glass A after a 2-hourexposure time to Murine Norovirus, Table 8 shows the results of Glass 56after a 2-hour exposure time to Murine Norovirus, Table 9 shows thecytotoxicity of Comparative Glass A and Glass 56 on RAW 264.7 cellcultures, and Table 10 shows the non-virucidal level of the test virusas measured on the cytotoxicity control samples for Comparative Glass Aand Glass 56.

TABLE 5 Input Virus Control and Antimicrobial Activity Control Results.Antimicrobial Activity Control Input Virus Replicate Replicate ReplicateDilution Control #1 #2 #3 Cell control 0 0 0 0 0 0 0 0 0 0 0 0 0 010⁻¹ + + NT NT NT 10⁻² + + + + + + + + + + + + + +10⁻³ + + + + + + + + + + + + + + 10⁻⁴ + + + + + + + + + + + + + +10⁻⁵ + + + + + + + + + + + + + + 10⁻⁶ + + 0 + + + + + 0 + + + + + 10⁻⁷ 00 0 0 0 0 0 0 0 0 0 0 0 0 10⁻⁸ 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PFU₅₀/250 μL10^(6.50) 10^(6.25) 10^(6.25) 10^(6.50) Mean PFU-₅₀/250 μL NA 10^(6.33)(+) = positive for presence of test virus (0) = No test virus recoveredand/or no cytotoxicity present (NA) = Not applicable (NT) = Not tested

TABLE 6 Cytotoxicity Control Results. Cytotoxicity Control (after 2 hourexposure time) Replicate Replicate Replicate Dilution #1 #2 #3 Cellcontrol 0 0 0 0 0 0 0 0 0 0 0 0 10⁻² + + + + + + + + + + + +10⁻³ + + + + + + + + + + + + 10⁻⁴ + + + + + + + + + + + +10⁻⁵ + + + + + + + + + + + + 10⁻⁶ 0 0 0 0 0 0 + 0 0 + 0 0 10⁻⁷ 0 0 0 0 00 0 0 0 0 0 0 10⁻⁸ 0 0 0 0 0 0 0 0 0 0 0 0 PFU₅₀/250 μL 10^(5.50)10^(5.75) 10^(5.75) Mean PFU-₅₀/250 μL 10^(5.67) (+) = positive forpresence of test virus (0) = No test virus recovered and/or nocytotoxicity present

TABLE 7 Results of Comparative Glass A after 2 hour exposure time toMurine Norovirus. Comparative Glass A - exposure to Murine NorovirusReplicate Replicate Replicate Dilution #1 #2 #3 Cell control 0 0 0 0 0 00 0 0 0 0 0 10⁻² + + + + + + + + + + + + 10⁻³ + + + + + + + + + + + +10⁻⁴ + + + + + + + + + + + + 10⁻⁵ + + + + + + + + + + + + 10⁻⁶ 0 + + 0 +0 0 + + + 0 0 10⁻⁷ 0 0 0 0 0 0 0 0 0 0 0 0 10⁻⁸ 0 0 0 0 0 0 0 0 0 0 0 0PFU₅₀/250 μL 10^(6.00) 10^(6.00) 10^(6.00) Mean PFU₅₀/250 μL 10^(6.00)Mean % reduction (based on No reduction cytotoxicity control) Mean Log₁₀Reduction (based on No reduction cytotoxicity control) Mean % reduction(based on 53.2% antimicrobial activity control) Mean Log₁₀ Reduction(based on 0.33 Log₁₀ antimicrobial activity control) (+) = positive forpresence of test virus (0) = No test virus recovered and/or nocytotoxicity present

TABLE 8 Results of Glass 56 after 2 hour exposure time to MurineNorovirus. Glass 56 - exposure to Murine Norovirus Replicate ReplicateReplicate Dilution #1 #2 #3 Cell control 0 0 0 0 0 0 0 0 0 0 0 010⁻² + + + + 0 0 0 0 0 0 0 0 10⁻³ + 0 + 0 0 0 0 0 0 0 0 0 10⁻⁴ 0 0 0 0 00 0 0 0 0 0 0 10⁻⁵ 0 0 0 0 0 0 0 0 0 0 0 0 10⁻⁶ 0 0 0 0 0 0 0 0 0 0 0 010⁻⁷ 0 0 0 0 0 0 0 0 0 0 0 0 10⁻⁸ 0 0 0 0 0 0 0 0 0 0 0 0 PFU₅₀/250 μL≤10^(3.00) ≤10^(1.50) ≤10^(1.50) Mean PFU₅₀/250 μL ≤10^(2.00) Mean %reduction (based on ≥99.98%  cytotoxicity control) Mean Log₁₀ Reduction(based on ≥3.67 Log₁₀ cytotoxicity control) Mean % reduction (based on≥99.995% antimicrobial activity control) Mean Log₁₀ Reduction (based on≥4.33 Log₁₀ antimicrobial activity control) (+) = positive for presenceof test virus (0) = No test virus recovered and/or no cytotoxicitypresent

TABLE 9 Cytotoxicity of Control Comparative Glass A and Control Glass 56on RAW 264.7 Cell Cultures. Cytotoxicity Control Comparative DilutionGlass A Glass 56 Cell control 0 0 0 0 10⁻² 0 0 0 0 10⁻³ 0 0 0 0 10⁻⁴ 0 00 0 10⁻⁵ 0 0 0 0 10⁻⁶ 0 0 0 0 10⁻⁷ 0 0 0 0 10⁻⁸ 0 0 0 0 TCD₅₀/250 μL≤10^(1.50) ≤10^(1.50) (0) = No test virus recovered and/or nocytotoxicity present

TABLE 10 Non-virucidal Level of Test Substance (Neutralization Control).Antimicrobial Activity + Cytotoxicity Control Comparative Dilution GlassA Glass 56 Cell control 0 0 0 0 10⁻² + + + + 10⁻³ + + + + 10⁻⁴ + + + +10⁻⁵ + + + + 10⁻⁶ + + + + 10⁻⁷ + + + + 10⁻⁸ + + + + (+) = Positive forthe presence of test virus after low titer stock virus added(neutralization control) (0) = No test virus recovered and/or nocytotoxicity present

Comparative Glass A exhibited a 0.33 log reduction in Murine Norovirus(or a 53.2% mean reduction), following a 2 hour exposure time at roomtemperature (20° C.) in a relative humidity of 42%, as compared to theantimicrobial activity control sample. Glass 56, however, exhibited agreater than 4.33 log reduction in Murine Norovirus (or 99.995% meanreduction or greater), following a 2 hour exposure time at roomtemperature (20° C.) in a relative humidity of 42%, as compared to theantimicrobial activity control sample.

Comparative Glass A did not demonstrate a mean reduction in viral titerof Murine Norovirus, following a 2 hour exposure time at roomtemperature (20° C.) in a relative humidity of 42%, in the presence of a5% fetal bovine serum organic soil load, as compared to the cytotoxicitycontrol sample. Glass 56, however, exhibited a greater than 3.67 meanlog reduction Murine Norovirus (or at least 99.98% or greater meanreduction), following a 2 hour exposure time at room temperature (20°C.) in a relative humidity of 42%, in the presence of a 5% fetal bovineserum organic soil load, as compared to the cytotoxicity control sample.

The results shown in Table 10 indicate that each test sample wasneutralized at a PFU₅₀/250 μL of ≤1.5 log₁₀.

Examples 12, 13 and 14 were formed into a powder and mixed withPolycrylic® at different loadings, based on Cu₂O content. The mixtureswere then coated onto Pyvek® paper (that was backed with a plastic filmbefore coated) through a brushing process and cured for 1 week. Thecoated paper was cut into coupons for testing under the EPA Test. FIGS.11 and 12 illustrate the results. FIG. 11 shows the antimicrobialperformance of the coupons, having different copper loadings. FIG. 12illustrates the antimicrobial performance of the composites with 15%Cu₂O.

Example 12 was ground into a powder and mixed with Pearlthane®polyurethane to provide a composite having different amounts of glass(by weight percent). The powdered glass and polyurethane were mixed at195-220° C. for several minutes. The resulting combination was made intoa 2.5 cm×2.5 cm coupon using melt processing, and evaluated forantimicrobial performance using the EPA Test. The results are providedin FIG. 13.

Injection molded articles were formed to evaluate antimicrobial activitywhen the surface is typically covered by a thin layer of matrix polymer.In such articles, the matrix polymer is typically hydrophobic and mayaffect antimicrobial performance. As shown in FIG. 14, surface treatmentcan improve antimicrobial performance. To prepare the injection moldedsamples, Example 12 was ground into a powder and mixed with Pearlthane®polyurethane to provide an injection moldable composite having 60 wt %glass. The composite was injection molded in a petri dish as shown inFIG. 14 to provide four injection molded samples (Samples A-D) that wereevaluated for antimicrobial performance using the EPA Test. Sample A wasnot subjected to surface treatment. Sample B was sanded to remove about10 mg of top surface of the sample. Samples C and D were subjected toplasma treatment using 100 W of power and pressure of 2 torr for 5minutes using two different gases, as shown in Table 11. FIG. 15 showsthe log reduction of Samples A-D.

TABLE 11 Table 11: Plasma Treatment condition for Samples C and D.Material Time, min Power, W Pressure, torr Gas Sample C 5 100 2 airSample D 5 100 2 N₂/H₂ (94/6% by volume)

As discussed herein, thermoplastic polymers may be utilized to form thearticles described herein through melt compounding processes. Articlesusing a thermoplastic polymer may also be formed by in situpolymerization and then into an article by a casting process. An epoxyresin (which is a thermosetting polymer) was used to demonstrate theconcept. The epoxy resin was made from Erisys GE22 and Amicure PACM,which were mixed well in presence of alcohol. Example 12 was ground intoa powder and added to the mixture according to Table 12, resulting in apaste-like material that was cast into a mold. In this example, a glassvial was used as a mold. The combination of the epoxy resin and groundglass was then cured at room temperature for a few days. The mold wasthen removed and the resulting article was dried at room temperature forone day and at 65° C. for a few hours.

TABLE 12 Table 12: Composition for making an article with epoxy resinand ground glass from Example 12. Materials Weight, parts Weight, partsWeight, parts Erisys GE22 1 1 3 Amicure PACM 0.3 0.3 1 Ethanol 6 5 2Example 12 15 10 10

Depending on the loading of the glass in the article, the resultingarticle may be porous or dense. The porosity increases with the increaseof glass loading as seen in Table 13, in which the water uptake by thearticles was measured after soaking the article in water for 2 minutes.Different articles were made from the same epoxy as used in Table 12 wascombined with different amounts of ground glass from Example 12. Thearticle was made using gel casting.

TABLE 13 Table 13: water uptake of articles using epoxy resin anddifferent loadings of ground glass from Example 12. Example 12 glassloading Water uptake in 2 minutes, (wt %/wt %) % 71 0.5 88 5.9 92 20.7

It will be apparent to those skilled in the art that variousmodifications and variations can be made without departing from thespirit or scope of the invention.

1. A glass comprising: SiO2 in a range from 50 mol % to 65 mol %; Al₂O₃in a range from 5 mol % to 20 mol %; P2O5 in a range from 5 mol % to 25mol %; and K₂O in a range from 5 mol % to 20 mol %.
 2. The glass ofclaim 1, wherein the range of SiO₂ is from 60 mol % to 65 mol %.
 3. Theglass of claim 2, wherein mol % of alkali metal oxide (R₂O) in the glassis greater than the Al₂O₃, wherein the R20 includes the K₂O and, ifpresent, Li₂O, Na₂O, Cs₂O, and/or Rb₂O.
 4. An electronic devicecomprising a housing and/or display, wherein the glass of claim 3 formsa sheet, and wherein the glass of claim 3 is part of the housing and/ordisplay.
 5. The glass of claim 1, wherein mol % of alkali metal oxide(R₂O) in the glass is greater than the Al₂O₃, wherein the R₂O includesthe K₂O and, if present, Li₂O, Na₂O, Cs₂O, and/or Rb₂O.
 6. An electronicdevice comprising a housing and/or display, wherein the glass of claim 1forms a sheet, and wherein the glass of claim 1 is part of the housingand/or display.